Synthesis method for carbosilanes

ABSTRACT

Si(OEt) 2 [CH 2 —Si(OEt) 3 ] 2  compounds are synthesized by reacting a Grignard reagent having the formula Si(OEt) 3 (CH 2 MgCl) with a quenching agent having the formula Si(OEt) 2 Cl 2 .

TECHNICAL FIELD

Disclosed are synthesis methods to produce carbosilanes.

BACKGROUND

Carbosilanes, i.e. linear or branched molecules with a backbone havingalternate Si and C atoms and at least one Si—C—Si unit, are attractingattention owing to their chemical properties and potential usage invarious fields such as ceramics, optical coatings, electronics,semiconductors, and hydrogen storage.

However, the synthesis of such compounds has proven to be relativelydifficult, partially due to the fact that a mixture of compounds may beproduced. In addition the low yield of such methods increases the costof making the targeted compound.

Controlled Si—C—Si unit synthesis has been achieved using a Grignardmethod. Gevorgyan et al. (J. Org. Chem. 418, 1991 C21-C23) disclose theformation of R₃Si—CH₂—Si(OCH2CH2)₃N from ClCH₂—Si(OCH₂CH₂)₃N and R₃Si—Clin the presence of magnesium in THF, with R₃ being Me₃, Me₂Ph, MePh₂,HMe₂, or HMePh. Brondani et al. (J. Org. Chem. 451, 1993 C1-C3) disclosecross-coupling of (tri-isopropyloxysilyl)methyl Grignard reagents withorganic halides to form trialkoxysilylated organic compounds. U.S. Pat.No. 5,153,295 to Whitmarsh et al. discloses that the diethylamino groupof a ClSi(NEt₂)₂CH₂Cl Grignard reagent blocks two chlorine sitespreventing branching of the carbosilane polymer. U.S. Pat. No. 6,730,802to Shen et al. discloses synthesis of2,4,6-trimethyl-2,4,6-trisilaheptane by reducingchloromethyl-dimethylchlorosilane with lithium aluminum hydride,reacting the resulting chloromethyldimethylsilane with magnesium to formthe corresponding Grignard reagent, and coupling the Grignard reagentwith methyldichlorosilane.

For some specific applications, obtaining a pure product is critical forthe stability of the process that uses the product, and suchnon-discriminating synthesis methods are costly since they involveexpensive separation processes to obtain the target compound. A needremains for a cost effective synthesis method of linear or branchedcarbosilanes.

NOTATION AND NOMENCLATURE

Certain abbreviations, symbols, and terms are used throughout thefollowing description and claims, and include:

As used herein, the term “carbosilane” refers to a linear or branchedmolecule with a backbone having alternate Si and C atoms and at leastone Si—C—Si unit; the term “Grignard reagent” refers to organomagnesiumhalides having the formula Si(OR′)_(x)H_(y)R_(z)(CH₂MgX), wherein x=0 to3; y=0 to 1; z=0 to 3; x+y+z=3; X═Cl, Br, or I; each R is independentlya C1 to C5 linear or branched alkyl group or a trimethylsilyl group; andeach R′ is independently a C1 to C5 linear or branched alkyl group, eventhough the claimed Grignard reagents are not used in a Grignardreaction; the term “quenching” refers to the reaction of the Grignardreagent with the quenching agent; the term “quenching agent” refers tothe compound that “deactivates” the Grignard reagent by reacting withthe Grignard reagent to produce a Mg salt compound.

As used herein, the term “alkyl group” refers to saturated functionalgroups containing exclusively carbon and hydrogen atoms. Further, theterm “alkyl group” refers to linear, branched, or cyclic alkyl groups.Examples of linear alkyl groups include without limitation, methylgroups, ethyl groups, propyl groups, butyl groups, pentyl groups, etc.Examples of branched alkyls groups include without limitation t-butyl.Examples of cyclic alkyl groups include without limitation, cyclopropylgroups, cyclopentyl groups, cyclohexyl groups, etc.

As used herein, the abbreviation “Me” refers to a methyl group; theabbreviation “Et” refers to an ethyl group; the abbreviation “Pr” refersto a n-propyl group; the abbreviation “Pr” refers to an isopropyl group;the abbreviation “nBu” refers to n-butyl, the abbreviation “tBu” refersto a tert-butyl; and the abbreviation “sBu” refers to a sec-butyl.

The standard abbreviations of the elements from the periodic table ofelements are used herein. It should be understood that elements may bereferred to by these abbreviations (e.g., Ni refers to nickel, Si refersto silicon, C refers to carbon, etc.).

SUMMARY

Disclosed are methods of synthesizing a carbosilane compound by reactinga Grignard reagent having the formula Si(OR′)_(x)H_(y)R_(z)(CH₂MgX) witha quenching agent having the formula SiCl_(a)(OR)_(b)(H)_(c) to produceSi(OR)_(b)(H)_(c)[CH₂—Si(OR′)_(x)H_(y)R_(z)]_(a), wherein a=1 to 3; b=0to 3; c=0 to 2; a+b+c=4; x=0 to 3; y=0 to 1; z=0 to 3; x+y+z=3; X═Cl,Br, or I; each R is independently a C1 to C5 linear or branched alkylgroup or a trimethylsilyl group; and each R′ is independently a C1 to C5linear or branched alkyl group. The disclosed methods may furtherinclude one or more of the following aspects:

-   -   a molar ratio of the Grignard reagent        Si(OR′)_(x)H_(y)R_(z)(CH₂MgX) to the quenching agent        SiCl_(a)(OR)_(b)(H)_(c) is between approximately 0.8 and        approximately 4.5;    -   forming the Grignard reagent Si(OR′)_(x)H_(y)R_(z)(CH₂MgX)        in-situ by reacting Si(OR′)_(x)H_(y)R_(z)(CH₂X) over magnesium;    -   the step of forming the Grignard reagent        Si(OR′)_(x)H_(y)R_(z)(CH₂MgX) occurring in a same vessel as the        step of reacting the Grignard reagent and the quenching agent;    -   reducing Si(OR)_(b)(H)_(c)[CH₂—Si(OR′)_(x)H_(y)R_(z)]_(a) by        AlLiH₄ in ether to form a compound having a formula        SiH_(b+c)[CH₂—SiH_(x+y)R_(z)]_(4−b−c), wherein b=0 to 3; c=0 to        2; b+c=1 to 3; x=0 to 3; y=0 to 1; z=0 to 3; x+y+z=3; and each R        is independently a C1 to C5 linear or branched alkyl group or a        trimethylsilyl group;    -   a molar ratio of AlLiH₄ to        Si(OR)_(b)(H)_(c)[CH₂—Si(OR′)_(x)H_(y)R_(z)]_(a) being between        approximately (b+ax)/4 and approximately (b+ax)/2, wherein b=0        to 3, a=1 to 3, and x=0 to 3;    -   reducing Si(OR)_(b)(H)_(c)[CH₂—Si(OR′)_(x)H_(y)R_(z)]_(a) by        NaBH₄ in ether to form SiH_(b+c)[CH₂—SiH_(x+y)R_(z)]_(4−b−c),        wherein b=0 to 3; c=0 to 2; b+c=1 to 3; x=0 to 3; y=0 to 1; z=0        to 3; x+y+z=3; and each R is independently a C1 to C5 linear or        branched alkyl group or a trimethylsilyl group;    -   a molar ratio of NaBH₄ to        Si(OR)_(b)(H)_(c)[CH₂—Si(OR′)_(x)H_(y)R_(z)]_(a) being between        approximately (b+ax)/4 and approximately (b+ax)/2, wherein b=0        to 3, a=1 to 3, and x=0 to 3;    -   x=3, y=0, z=0, and R′=Me or Et;    -   the Grignard reagent being Si(OR′)₃(CH₂MgCl);    -   a=2, b=2, and c=0;    -   the quenching agent being Si(OEt)₂Cl₂;    -   y=1 and b=0;    -   z=0 and c=2;    -   the quenching agent being SiH₂Cl₂; and    -   b=0 and c=2.

Also disclosed are methods of synthesizing a carbosilane compound by insitu quenching of a Grignard reagent having the formulaSi(OR′)_(x)H_(y)R_(z)(CH₂MgX) with a quenching agent having the formulaSiCl_(a)(OR)_(b)(H)_(c) to produceSi(OR)_(b)(H)_(c)[CH₂—Si(OR′)_(x)H_(y)R_(z)]_(a), wherein a=1 to 3; b=0to 3; c=0 to 2; a+b+c=4; x=0 to 3; y=0 to 1; z=0 to 3; x+y+z=3; X═Cl,Br, or I; each R is independently a C1 to C5 linear or branched alkylgroup or a trimethylsilyl group; and each R′ is independently a C1 to C5linear or branched alkyl group.

Also disclosed are methods of synthesizing a carbolsilane compound byreacting a Grignard reagent having the formula Si(OEt)₃(CH₂MgCl) with aquenching agent having the formula Si(OEt)₂Cl₂ to produceSi(OEt)₂[CH₂—Si(OEt)₃]₂. The disclosed methods may further include oneor more of the following aspects:

-   -   forming the Grignard reagent Si(OEt)₃(CH₂MgCl) by reacting        Si(OEt)₃(CH₂X) over magnesium;    -   the step of forming the Grignard reagent Si(OEt)₃(CH₂MgCl)        occurring in a same vessel as the step of reacting the Grignard        reagent and the quenching agent; and    -   reducing Si(OEt)₂[CH₂—Si(OEt)₃]₂ to form a compound having a        formula SiH₂[CH₂—SiH₃]₂.

BRIEF DESCRIPTION OF THE FIGURES

For a further understanding of the nature and objects of the presentinvention, reference should be made to the following detaileddescription, taken in conjunction with the accompanying figure wherein:

FIG. 1 is a gas chromatograph/mass spectrometer (GC/MS) graph of theproduct synthesized in the Comparative Example; and

FIG. 2 is a GC/MS graph of the product synthesized in the Example.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Disclosed are methods of synthesizing compounds having the formulaSi(OR)_(b)(H)_(c)[CH₂—Si(OR′)_(x)H_(y)R_(z)]_(a), wherein a=1 to 3; b=0to 3; c=0 to 2; a+b+c=4; x=0 to 3; y=0 to 1; z=0 to 3; x+y+z=3; each Ris independently a C1 to C5 linear or branched alkyl group or atrimethylsilyl group; and each R′ is independently a C1 to C5 linear orbranched alkyl group. These compounds may be used in the field ofceramics, optical coatings, electronics (i.e., devices), semiconductors(i.e., components), hydrogen storage, and semiconductor components thatmay be used at least in electronic devices.

In some embodiments, x=3, y=0, z=0, and R′=Me or Et to produceSi(OR)_(b)(H)_(c)[CH₂—Si(OMe)₃]_(a) andSi(OR)_(b)(H)_(c)[CH₂—Si(OEt)₃]_(a), wherein a=1 to 3; b=0 to 3; c=0 to2; a+b+c=4; and each R is independently a C1 to C5 linear or branchedalkyl group or a trimethylsilyl (SiMe₃) group.

Exemplary compounds wherein x=3, y=0, z=0, R′=Me or Et, a=3, b=0, andc=1 include SiH[CH₂—Si(OMe)₃]₃ and SiH[CH₂—Si(OEt)₃]₃.

Exemplary compounds wherein x=3, y=0, z=0, R′=Me or Et, a=3, b=1, andc=0 include Si(OMe)[CH₂—Si(OMe)₃]₃, Si(OMe)[CH₂—Si(OEt)₃]₃,Si(OEt)[CH₂—Si(OMe)₃]₃, Si(OEt)[CH₂—Si(OEt)₃]₃, Si(OiPr)[CH₂—Si(OMe)₃]₃,Si(OiPr)[CH₂—Si(OEt)₃]₃, Si(OnPr)[CH₂—Si(OMe)₃]₃,Si(OnPr)[CH₂—Si(OEt)₃]₃, Si(OnBu)[CH₂—Si(OMe)₃]₃,Si(OnBu)[CH₂—Si(OEt)₃]₃, Si(OtBu)[CH₂—Si(OMe)₃]₃,Si(OtBu)[CH₂—Si(OEt)₃]₃, Si(OiBu)[CH₂—Si(OMe)₃]₃,Si(OiBu)[CH₂—Si(OEt)₃]₃, Si(OSiMe₃)[CH₂—Si(OMe)₃]₃, andSi(OSiMe₃)[CH₂—Si(OEt)₃]₃.

Exemplary compounds wherein x=3, y=0, z=0, R′=Me or Et, a=2, b=0, andc=2 include SiH₂[CH₂—Si(OMe)₃]₂ and SiH₂[CH₂—Si(OEt)₃]₂.

Exemplary compounds wherein x=3, y=0, z=0, R′=Me or Et, a=2, b=2, andc=0 include Si(OMe)₂[CH₂—Si(OMe)₃]₂, Si(OMe)₂[CH₂—Si(OEt)₃]₂,Si(OEt)₂[CH₂—Si(OMe)₃]₂, Si(OEt)₂[CH₂—Si(OEt)₃]₂,Si(OiPr)₂[CH₂—Si(OMe)₃]₂, Si(OiPr)₂[CH₂—Si(OEt)₃]₂,Si(OnPr)₂[CH₂—Si(OMe)₃]₂, Si(OnPr)₂[CH₂—Si(OEt)₃]₂,Si(OnBu)₂[CH₂—Si(OMe)₃]₂, Si(OnBu)₂[CH₂—Si(OEt)₃]₂,Si(OtBu)₂[CH₂—Si(OMe)₃]₂, Si(OtBu)₂[CH₂—Si(OEt)₃]₂,Si(OiBu)₂[CH₂—Si(OMe)₃]₂, Si(OiBu)₂[CH₂—Si(OEt)₃]₂,Si(OSiMe₃)₂[CH₂—Si(OMe)₃]₂ and Si(OSiMe₃)₂[CH₂—Si(OEt)₃]₂.

Exemplary compounds wherein x=3, y=0, z=0, R′=Me or Et, a=2, b=1, andc=1 include SiH(OMe)[CH₂—Si(OMe)₃]₂, SiH(OMe)[CH₂—Si(OEt)₃]₂,SiH(OEt)[CH₂—Si(OMe)₃]₂, SiH(OEt)[CH₂—Si(OEt)₃]₂,SiH(OiPr)[CH₂—Si(OMe)₃]₂, SiH(OiPr)[CH₂—Si(OEt)₃]₂,SiH(OnPr)[CH₂—Si(OMe)₃]₂, SiH(OnPr)[CH₂—Si(OEt)₃]₂,SiH(OnBu)[CH₂—Si(OMe)₃]₂, SiH(OnBu)[CH₂—Si(OEt)₃]₂,SiH(OtBu)[CH₂—Si(OMe)₃]₂, SiH(OtBu)[CH₂—Si(OEt)₃]₂,SiH(OiBu)[CH₂—Si(OMe)₃]₂, SiH(OiBu)[CH₂—Si(OEt)₃]₂,SiH₂(OSiMe₃)[CH₂—Si(OMe)₃]₂, and SiH(OSiMe₃)[CH₂—Si(OEt)₃]₂.

Exemplary compounds wherein x=3, y=0, z=0, R′=Me or Et, a=1, b=1, andc=2 include SiH₂(OMe)[CH₂—Si(OMe)₃], SiH₂(OMe)[CH₂—Si(OEt)₃],SiH₂(OEt)[CH₂—Si(OMe)₃], SiH₂(OEt)[CH₂—Si(OEt)₃],SiH₂(OiPr)[CH₂—Si(OMe)₃], SiH₂(OiPr)[CH₂—Si(OEt)₃],SiH₂(OnPr)[CH₂—Si(OMe)₃], SiH₂(OnPr)[CH₂—Si(OEt)₃],SiH₂(OnBu)[CH₂—Si(OMe)₃], SiH₂(OnBu)[CH₂—Si(OEt)₃],SiH₂(OtBu)[CH₂—Si(OMe)₃], SiH₂(OtBu)[CH₂—Si(OEt)₃],SiH₂(OiBu)[CH₂—Si(OMe)₃], SiH₂(OiBu)[CH₂—Si(OEt)₃],SiH₂(OSiMe₃)[CH₂—Si(OMe)₃], and SiH₂(OSiMe₃)[CH₂—Si(OEt)₃].

Exemplary compounds wherein x=3, y=0, z=0, R′=Me or Et, a=1, b=2, andc=1 include SiH(OMe)₂[CH₂—Si(OMe)₃], SiH(OMe)₂[CH₂—Si(OEt)₃],SiH(OEt)₂[CH₂—Si(OMe)₃], SiH(OEt)₂[CH₂—Si(OEt)₃],SiH(OiPr)₂[CH₂—Si(OMe)₃], SiH(OiPr)₂[CH₂—Si(OEt)₃],SiH(OnPr)₂[CH₂—Si(OMe)₃], SiH(OnPr)₂[CH₂—Si(OEt)₃],SiH(OnBu)₂[CH₂—Si(OMe)₃], SiH(OnBu)₂[CH₂—Si(OEt)₃],SiH(OtBu)₂[CH₂—Si(OMe)₃], SiH(OtBu)₂[CH₂—Si(OEt)₃],SiH(OiBu)₂[CH₂—Si(OMe)₃], SiH(OiBu)₂[CH₂—Si(OEt)₃],SiH(OSiMe₃)₂[CH₂—Si(OMe)₃], and SiH(OSiMe₃)₂[CH₂—Si(OEt)₃].

Exemplary compounds wherein x=3, y=0, z=0, R′=Me or Et, a=1, b=3, andc=0 include Si(OMe)₃[CH₂—Si(OMe)₃], Si(OMe)₃[CH₂—Si(OEt)₃],Si(OEt)₃[CH₂—Si(OMe)₃], Si(OEt)₃[CH₂—Si(OEt)₃], Si(OiPr)₃[CH₂—Si(OMe)₃],Si(OiPr)₃[CH₂—Si(OEt)₃], Si(OnPr)₃[CH₂—Si(OMe)₃],Si(OnPr)₃[CH₂—Si(OEt)₃], Si(OnBu)₃[CH₂—Si(OMe)₃],Si(OnBu)₃[CH₂—Si(OEt)₃], Si(OtBu)₃[CH₂—Si(OMe)₃],Si(OtBu)₃[CH₂—Si(OEt)₃], Si(OiBu)₃[CH₂—Si(OMe)₃],Si(OiBu)₃[CH₂—Si(OEt)₃], Si(OSiMe₃)₃[CH₂—Si(OMe)₃], andSi(OSiMe₃)₃[CH₂—Si(OEt)₃].

In some embodiments, a=2, b=2, and c=0 to produceSi(OR)₂[CH₂—Si(OR′)_(x)H_(y)R_(z)]₂, wherein x=0 to 3; y=0 to 1; z=0 to3; x+y+z=3; each R is independently a C1 to C5 linear or branched alkylgroup or a trimethylsilyl group; and each R′ is independently a C1 to C5linear or branched alkyl group.

Exemplary compounds wherein a=2, b=2, c=0, x=3, y=0, and z=0 includeSi(OMe)₂[CH₂—Si(OMe)₃]₂, Si(OMe)₂[CH₂—Si(OEt)₃]₂,Si(OMe)₂[CH₂—Si(OiPr)₃]₂, Si(OMe)₂[CH₂—Si(OnPr)₃]₂,Si(OMe)₂[CH₂—Si(OnBu)₃]₂, Si(OMe)₂[CH₂—Si(OtBu)₃]₂,Si(OMe)₂[CH₂—Si(OiBu)₃]₂, Si(OEt)₂[CH₂—Si(OMe)₃]₂,Si(OEt)₂[CH₂—Si(OEt)₃]₂, Si(OEt)₂[CH₂—Si(OiPr)₃]₂,Si(OEt)₂[CH₂—Si(OnPr)₃]₂, Si(OEt)₂[CH₂—Si(OnBu)₃]₂,Si(OEt)₂[CH₂—Si(OtBu)₃]₂, Si(OEt)₂[CH₂—Si(OiBu)₃]₂,Si(OiPr)₂[CH₂—Si(OMe)₃]₂, Si(OiPr)₂[CH₂—Si(OEt)₃]₂,Si(OiPr)₂[CH₂—Si(OiPr)₃]₂, Si(OiPr)₂[CH₂—Si(OnPr)₃]₂,Si(OiPr)₂[CH₂—Si(OnBu)₃]₂, Si(OiPr)₂[CH₂—Si(OtBu)₃]₂,Si(OiPr)₂[CH₂—Si(OiBu)₃]₂, Si(OnPr)₂[CH₂—Si(OMe)₃]₂,Si(OnPr)₂[CH₂—Si(OEt)₃]₂, Si(OnPr)₂[CH₂—Si(OiPr)₃]₂,Si(OnPr)₂[CH₂—Si(OnPr)₃]₂, Si(OnPr)₂[CH₂—Si(OnBu)₃]₂,Si(OnPr)₂[CH₂—Si(OtBu)₃]₂, Si(OnPr)₂[CH₂—Si(OiBu)₃]₂,Si(OnBu)₂[CH₂—Si(OMe)₃]₂, Si(OnBu)₂[CH₂—Si(OEt)₃]₂,Si(OnBu)₂[CH₂—Si(OiPr)₃]₂, Si(OnBu)₂[CH₂—Si(OnPr)₃]₂,Si(OnBu)₂[CH₂—Si(OnBu)₃]₂, Si(OnBu)₂[CH₂—Si(OtBu)₃]₂,Si(OnBu)₂[CH₂—Si(OiBu)₃]₂, Si(OtBu)₂[CH₂—Si(OMe)₃]₂,Si(OtBu)₂[CH₂—Si(OEt)₃]₂, Si(OtBu)₂[CH₂—Si(OiPr)₃]₂,Si(OtBu)₂[CH₂—Si(OnPr)₃]₂, Si(OtBu)₂[CH₂—Si(OnBu)₃]₂,Si(OtBu)₂[CH₂—Si(OtBu)₃]₂, Si(OtBu)₂[CH₂—Si(OiBu)₃]₂,Si(OiBu)₂[CH₂—Si(OMe)₃]₂, Si(OiBu)₂[CH₂—Si(OEt)₃]₂,Si(OiBu)₂[CH₂—Si(OiPr)₃]₂, Si(OiBu)₂[CH₂—Si(OnPr)₃]₂,Si(OiBu)₂[CH₂—Si(OnBu)₃]₂, Si(OiBu)₂[CH₂—Si(OtBu)₃]₂,Si(OiBu)₂[CH₂—Si(OiBu)₃]₂, Si(OSiMe₃)₂[CH₂—Si(OMe)₃]₂,Si(OSiMe₃)₂[CH₂—Si(OEt)₃]₂, Si(OSiMe₃)₂[CH₂—Si(OiPr)₃]₂,Si(OSiMe₃)₂[CH₂—Si(OnPr)₃]₂, Si(OSiMe₃)₂[CH₂—Si(OnBu)₃]₂,Si(OSiMe₃)₂[CH₂—Si(OiBu)₃]₂, and Si(OSiMe₃)₂[CH₂—Si(OtBu)₃]₂.

Exemplary compounds wherein a=2, b=2, c=0, x=2, y=1, and z=0 includeSi(OMe)₂[CH₂—SiH(OMe)₂]₂, Si(OMe)₂[CH₂—SiH(OEt)₂]₂,Si(OMe)₂[CH₂—SiH(OiPr)₂]₂, Si(OMe)₂[CH₂—SiH(OnPr)₂]₂,Si(OMe)₂[CH₂—SiH(OnBu)₂]₂, Si(OMe)₂[CH₂—SiH(OtBu)₂]₂,Si(OMe)₂[CH₂—SiH(OiBu)₂]₂, Si(OEt)₂[CH₂—SiH(OMe)₂]₂,Si(OEt)₂[CH₂—SiH(OEt)₂]₂, Si(OEt)₂[CH₂—SiH(OiPr)₂]₂,Si(OEt)₂[CH₂—SiH(OnPr)₂]₂, Si(OEt)₂[CH₂—SiH(OnBu)₂]₂,Si(OEt)₂[CH₂—SiH(OtBu)₂]₂, Si(OEt)₂[CH₂—SiH(OiBu)₂]₂,Si(OiPr)₂[CH₂—SiH(OMe)₂]₂, Si(OiPr)₂[CH₂—SiH(OEt)₂]₂,Si(OiPr)₂[CH₂—SiH(OiPr)₂]₂, Si(OiPr)₂[CH₂—SiH(OnPr)₂]₂,Si(OiPr)₂[CH₂—SiH(OnBu)₂]₂, Si(OiPr)₂[CH₂—SiH(OtBu)₂]₂,Si(OiPr)₂[CH₂—SiH(OiBu)₂]₂, Si(OnPr)₂[CH₂—SiH(OMe)₂]₂,Si(OnPr)₂[CH₂—SiH(OEt)₂]₂, Si(OnPr)₂[CH₂—SiH(OiPr)₂]₂,Si(OnPr)₂[CH₂—SiH(OnPr)₂]₂, Si(OnPr)₂[CH₂—SiH(OnBu)₂]₂,Si(OnPr)₂[CH₂—SiH(OtBu)₂]₂, Si(OnPr)₂[CH₂—SiH(OiBu)₂]₂,Si(OnBu)₂[CH₂—SiH(OMe)₂]₂, Si(OnBu)₂[CH₂—SiH(OEt)₂]₂,Si(OnBu)₂[CH₂—SiH(OiPr)₂]₂, Si(OnBu)₂[CH₂—SiH(OnPr)₂]₂,Si(OnBu)₂[CH₂—SiH(OnBu)₂]₂, Si(OnBu)₂[CH₂—SiH(OiBu)₂]₂,Si(OnBu)₂[CH₂—SiH(OtBu)₂]₂, Si(OtBu)₂[CH₂—SiH(OMe)₂]₂,Si(OtBu)₂[CH₂—SiH(OEt)₂]₂, Si(OtBu)₂[CH₂—SiH(OiPr)₂]₂,Si(OtBu)₂[CH₂—SiH(OnPr)₂]₂, Si(OtBu)₂[CH₂—SiH(OnBu)₂]₂,Si(OtBu)₂[CH₂—SiH(OtBu)₂]₂, Si(OtBu)₂[CH₂—SiH(OiBu)₂]₂,Si(OiBu)₂[CH₂—SiH(OMe)₂]₂, Si(OiBu)₂[CH₂—SiH(OEt)₂]₂,Si(OiBu)₂[CH₂—SiH(OnPr)₂]₂, Si(OiBu)₂[CH₂—SiH(OiPr)₂]₂,Si(OiBu)₂[CH₂—SiH(OnBu)₂]₂, Si(OiBu)₂[CH₂—SiH(OtBu)₂]₂,Si(OiBu)₂[CH₂—SiH(OiBu)₂]₂, Si(OSiMe₃)₂[CH₂—SiH(OMe)₂]₂,Si(OSiMe₃)₂[CH₂—SiH(OEt)₂]₂, Si(OSiMe₃)₂[CH₂—SiH(OiPr)₂]₂,Si(OSiMe₃)₂[CH₂—SiH(OnPr)₂]₂, Si(OSiMe₃)₂[CH₂—SiH(OnBu)₂]₂,Si(OSiMe₃)₂[CH₂—SiH(OtBu)₂]₂, and Si(OSiMe₃)₂[CH₂—SiH(OiBu)₂]₂.

Exemplary compounds wherein a=2, b=2, c=0, x=2, y=0, and z=1 includeSi(OMe)₂[CH₂—SiMe(OMe)₂]₂, Si(OMe)₂[CH₂—SiMe(OEt)₂]₂,Si(OMe)₂[CH₂—SiMe(OiPr)₂]₂, Si(OMe)₂[CH₂—SiMe(OnPr)₂]₂,Si(OMe)₂[CH₂—SiMe(OnBu)₂]₂, Si(OMe)₂[CH₂—SiMe(OtBu)₂]₂,Si(OMe)₂[CH₂—SiMe(OiBu)₂]₂, Si(OEt)₂[CH₂—SiMe(OMe)₂]₂,Si(OEt)₂[CH₂—SiMe(OEt)₂]₂, Si(OEt)₂[CH₂—SiMe(OiPr)₂]₂,Si(OEt)₂[CH₂—SiMe(OnPr)₂]₂, Si(OEt)₂[CH₂—SiMe(OnBu)₂]₂,Si(OEt)₂[CH₂—SiMe(OtBu)₂]₂, Si(OEt)₂[CH₂—SiMe(OiBu)₂]₂,Si(OiPr)₂[CH₂—SiMe(OMe)₂]₂, Si(OiPr)₂[CH₂—SiMe(OEt)₂]₂,Si(OiPr)₂[CH₂—SiMe(OiPr)₂]₂, Si(OiPr)₂[CH₂—SiMe(OnPr)₂]₂,Si(OiPr)₂[CH₂—SiMe(OnBu)₂]₂, Si(OiPr)₂[CH₂—SiMe(OtBu)₂]₂,Si(OiPr)₂[CH₂—SiMe(OiBu)₂]₂, Si(OnPr)₂[CH₂—SiMe(OMe)₂]₂,Si(OnPr)₂[CH₂—SiMe(OEt)₂]₂, Si(OnPr)₂[CH₂—SiMe(OiPr)₂]₂,Si(OnPr)₂[CH₂—SiMe(OnPr)₂]₂, Si(OnPr)₂[CH₂—SiMe(OnBu)₂]₂,Si(OnPr)₂[CH₂—SiMe(OtBu)₂]₂, Si(OnPr)₂[CH₂—SiMe(OiBu)₂]₂,Si(OnBu)₂[CH₂—SiMe(OMe)₂]₂, Si(OnBu)₂[CH₂—SiMe(OEt)₂]₂,Si(OnBu)₂[CH₂—SiMe(OiPr)₂]₂, Si(OnBu)₂[CH₂—SiMe(OnPr)₂]₂,Si(OnBu)₂[CH₂—SiMe(OnBu)₂]₂, Si(OnBu)₂[CH₂—SiMe(OiBu)₂]₂,Si(OnBu)₂[CH₂—SiMe(OtBu)₂]₂, Si(OtBu)₂[CH₂—SiMe(OMe)₂]₂,Si(OtBu)₂[CH₂—SiMe(OEt)₂]₂, Si(OtBu)₂[CH₂—SiMe(OiPr)₂]₂,Si(OtBu)₂[CH₂—SiMe(OnPr)₂]₂, Si(OtBu)₂[CH₂—SiMe(OnBu)₂]₂,Si(OtBu)₂[CH₂—SiMe(OtBu)₂]₂, Si(OtBu)₂[CH₂—SiMe(OiBu)₂]₂,Si(OiBu)₂[CH₂—SiMe(OMe)₂]₂, Si(OiBu)₂[CH₂—SiMe(OEt)₂]₂,Si(OiBu)₂[CH₂—SiMe(OnPr)₂]₂, Si(OiBu)₂[CH₂—SiMe(OiPr)₂]₂,Si(OiBu)₂[CH₂—SiMe(OnBu)₂]₂, Si(OiBu)₂[CH₂—SiMe(OtBu)₂]₂,Si(OiBu)₂[CH₂—SiMe(OiBu)₂]₂, Si(OSiMe₃)₂[CH₂—SiMe(OMe)₂]₂,Si(OSiMe₃)₂[CH₂—SiMe(OEt)₂]₂, Si(OSiMe₃)₂[CH₂—SiMe(OiPr)₂]₂,Si(OSiMe₃)₂[CH₂—SiMe(OnPr)₂]₂, Si(OSiMe₃)₂[CH₂—SiMe(OnBu)₂]₂,Si(OSiMe₃)₂[CH₂—SiMe(OtBu)₂]₂, and Si(OSiMe₃)₂[CH₂—SiMe(OiBu)₂]₂.

Exemplary compounds wherein a=2, b=2, c=0, x=1, y=1, and z=1 includeSi(OMe)₂[CH₂—SiHMe(OMe)]₂, Si(OMe)₂[CH₂—SiHMe(OEt)]₂,Si(OMe)₂[CH₂—SiHMe(OiPr)]₂, Si(OMe)₂[CH₂—SiHMe(OnPr)]₂,Si(OMe)₂[CH₂—SiHMe(OnBu)]₂, Si(OMe)₂[CH₂—SiHMe(OtBu)]₂,Si(OMe)₂[CH₂—SiHMe(OiBu)]₂, Si(OEt)₂[CH₂—SiHMe(OMe)]₂,Si(OEt)₂[CH₂—SiHMe(OEt)]₂, Si(OEt)₂[CH₂—SiHMe(OiPr)]₂,Si(OEt)₂[CH₂—SiHMe(OnPr)]₂, Si(OEt)₂[CH₂—SiHMe(OnBu)]₂,Si(OEt)₂[CH₂—SiHMe(OtBu)]₂, Si(OEt)₂[CH₂—SiHMe(OiBu)]₂,Si(OiPr)₂[CH₂—SiHMe(OMe)]₂, Si(OiPr)₂[CH₂—SiHMe(OEt)]₂,Si(OiPr)₂[CH₂—SiHMe(OiPr)]₂, Si(OiPr)₂[CH₂—SiHMe(OnPr)]₂,Si(OiPr)₂[CH₂—SiHMe(OnBu)]₂, Si(OiPr)₂[CH₂—SiHMe(OtBu)]₂,Si(OiPr)₂[CH₂—SiHMe(OiBu)]₂, Si(OnPr)₂[CH₂—SiHMe(OMe)]₂,Si(OnPr)₂[CH₂—SiHMe(OEt)]₂, Si(OnPr)₂[CH₂—SiHMe(OiPr)]₂,Si(OnPr)₂[CH₂—SiHMe(OnPr)]₂, Si(OnPr)₂[CH₂—SiHMe(OnBu)]₂,Si(OnPr)₂[CH₂—SiHMe(OtBu)]₂, Si(OnPr)₂[CH₂—SiHMe(OiBu)]₂,Si(OnBu)₂[CH₂—SiHMe(OMe)]₂, Si(OnBu)₂[CH₂—SiHMe(OEt)]₂,Si(OnBu)₂[CH₂—SiHMe(OiPr)]₂, Si(OnBu)₂[CH₂—SiHMe(OnPr)]₂,Si(OnBu)₂[CH₂—SiHMe(OnBu)]₂, Si(OnBu)₂[CH₂—SiHMe(OiBu)]₂,Si(OnBu)₂[CH₂—SiHMe(OtBu)]₂, Si(OtBu)₂[CH₂—SiHMe(OMe)]₂,Si(OtBu)₂[CH₂—SiHMe(OEt)]₂, Si(OtBu)₂[CH₂—SiHMe(OiPr)]₂,Si(OtBu)₂[CH₂—SiHMe(OnPr)]₂, Si(OnBu)₂[CH₂—SiHMe(OnBu)]₂,Si(OtBu)₂[CH₂—SiHMe(OtBu)]₂, Si(OtBu)₂[CH₂—SiHMe(OiBu)]₂,Si(OiBu)₂[CH₂—SiHMe(OMe)]₂, Si(OiBu)₂[CH₂—SiHMe(OEt)]₂,Si(OiBu)₂[CH₂—SiHMe(OnPr)]2, Si(OiBu)₂[CH₂—SiHMe(OiPr)]₂,Si(OiBu)₂[CH₂—SiHMe(OnBu)]₂, Si(OiBu)₂[CH₂—SiHMe(OtBu)]₂,Si(OiBu)₂[CH₂—SiHMe(OiBu)]₂, Si(OSiMe₃)₂[CH₂—SiHMe(OMe)]₂,Si(OSiMe₃)₂[CH₂—SiHMe(OEt)]₂, Si(OSiMe₃)₂[CH₂—SiHMe(OiPr)]₂,Si(OSiMe₃)₂[CH₂—SiHMe(OnPr)]₂, Si(OSiMe₃)₂[CH₂—SiHMe(OnBu)]₂,Si(OSiMe₃)₂[CH₂—SiHMe(OtBu)]₂, and Si(OSiMe₃)₂[CH₂—SiHMe(OiBu)]₂.

Exemplary compounds wherein a=2, b=2, c=0, x=1, y=0, and z=2 includeSi(OMe)₂[CH₂—SiMe₂(OMe)]₂, Si(OMe)₂[CH₂—SiMe₂(OEt)]₂,Si(OMe)₂[CH₂—SiMe₂(OiPr)]₂, Si(OMe)₂[CH₂—SiMe₂(OnPr)]₂,Si(OMe)₂[CH₂—SiMe₂(OnBu)]₂, Si(OMe)₂[CH₂—SiMe₂(OtBu)]₂,Si(OMe)₂[CH₂—SiMe₂(OiBu)]₂, Si(OEt)₂[CH₂—SiMe₂(OMe)]₂,Si(OEt)₂[CH₂—SiMe₂(OEt)]₂, Si(OEt)₂[CH₂—SiMe₂(OiPr)]₂,Si(OEt)₂[CH₂—SiMe₂(OnPr)]₂, Si(OEt)₂[CH₂—SiMe₂(OnBu)]₂,Si(OEt)₂[CH₂—SiMe₂(OtBu)]₂, Si(OEt)₂[CH₂—SiMe₂(OiBu)]₂,Si(OiPr)₂[CH₂—SiMe₂(OMe)]₂, Si(OiPr)₂[CH₂—SiMe₂(OEt)]₂,Si(OiPr)₂[CH₂—SiMe₂(OiPr)]₂, Si(OiPr)₂[CH₂—SiMe₂(OnPr)]₂,Si(OiPr)₂[CH₂—SiMe₂(OnBu)]₂, Si(OiPr)₂[CH₂—SiMe₂(OtBu)]₂,Si(OnPr)₂[CH₂—SiMe₂(OiBu)]₂, Si(OnPr)₂[CH₂—SiMe₂(OMe)]₂,Si(OnPr)₂[CH₂—SiMe₂(OEt)]₂, Si(OnPr)₂[CH₂—SiMe₂(OiPr)]₂,Si(OnPr)₂[CH₂—SiMe₂(OnPr)]₂, Si(OnPr)₂[CH₂—SiMe₂(OnBu)]₂,Si(OnPr)₂[CH₂—SiMe₂(OtBu)]₂, Si(OnPr)₂[CH₂—SiMe₂(OiBu)]₂,Si(OnBu)₂[CH₂—SiMe₂(OMe)]₂, Si(OnBu)₂[CH₂—SiMe₂(OEt)]₂,Si(OnBu)₂[CH₂—SiMe₂(OiPr)]₂, Si(OnBu)₂[CH₂—SiMe₂(OnPr)]₂,Si(OnBu)₂[CH₂—SiMe₂(OnBu)]₂, Si(OnBu)₂[CH₂—SiMe₂(OiBu)]₂,Si(OnBu)₂[CH₂—SiMe₂(OtBu)]₂, Si(OtBu)₂[CH₂—SiMe₂(OMe)]₂,Si(OtBu)₂[CH₂—SiMe₂(OEt)]₂, Si(OtBu)₂[CH₂—SiMe₂(OiPr)]₂,Si(OtBu)₂[CH₂—SiMe₂(OnPr)]₂, Si(OtBu)₂[CH₂—SiMe₂(OnBu)]₂,Si(OtBu)₂[CH₂—SiMe₂(OtBu)]₂, Si(OtBu)₂[CH₂—SiMe₂(OiBu)]₂,Si(OiBu)₂[CH₂—SiMe₂(OMe)]₂, Si(OiBu)₂[CH₂—SiMe₂(OEt)]₂,Si(OiBu)₂[CH₂—SiMe₂(OnPr)]₂, Si(OiBu)₂[CH₂—SiMe₂(OiPr)]₂,Si(OiBu)₂[CH₂—SiMe₂(OnBu)]₂, Si(OiBu)₂[CH₂—SiMe₂(OtBu)]₂,Si(OiBu)₂[CH₂—SiMe₂(OiBu)]₂, Si(OSiMe₃)₂[CH₂—SiMe₂(OMe)]₂,Si(OSiMe₃)₂[CH₂—SiMe₂(OEt)]₂, Si(OSiMe₃)₂[CH₂—SiMe₂(OiPr)]₂,Si(OSiMe₃)₂[CH₂—SiMe₂(OnPr)]₂, Si(OSiMe₃)₂[CH₂—SiMe₂(OnBu)]₂,Si(OSiMe₃)₂[CH₂—SiMe₂(OtBu)]₂, and Si(OSiMe₃)₂[CH₂—SiMe₂(OiBu)]₂.

Exemplary compounds wherein a=2, b=2, c=0, x=0, y=1, and z=2 includeSi(OMe)₂[CH₂—SiHMe₂]₂, Si(OMe)₂[CH₂—SiHEt₂]₂, Si(OMe)₂[CH₂—SiH(iPr)₂]₂,Si(OMe)₂[CH₂—SiH(nPr)₂]₂, Si(OMe)₂[CH₂—SiH(nBu)₂]₂,Si(OMe)₂[CH₂—SiH(OtBu)₂]₂, Si(OMe)₂[CH₂—SiH(iBu)₂]₂,Si(OMe)₂[CH₂—SiH(SiMe₃)₂]₂, Si(OEt)₂[CH₂—SiHMe₂]₂,Si(OEt)₂[CH₂—SiHEt₂]₂, Si(OEt)₂[CH₂—SiH(iPr)₂]₂,Si(OEt)₂[CH₂—Si(nPr)₂]₂, Si(OEt)₂[CH₂—SiH(nBu)₂]₂,Si(OEt)₂[CH₂—SiH(OtBu)₂]₂, Si(OEt)₂[CH₂—SiH(iBu)₂]₂,Si(OEt)₂[CH₂—SiH(SiMe₃)₂]₂, Si(OiPr)₂[CH₂—SiHMe₂]₂,Si(OiPr)₂[CH₂—SiHEt₂]₂, Si(OiPr)₂[CH₂—SiH(iPr)₂]₂,Si(OiPr)₂[CH₂—SiH(nPr)₂]₂, Si(OiPr)₂[CH₂—SiH(nBu)₂]₂,Si(OiPr)₂[CH₂—SiH(OtBu)₂]₂, Si(OiPr)₂[CH₂—SiH(iBu)₂]₂,Si(OiPr)₂[CH₂—SiH(SiMe₃)₂]₂, Si(OnPr)₂[CH₂—SiHMe₂]₂,Si(OnPr)₂[CH₂—SiHEt₂]₂, Si(OnPr)₂[CH₂—SiH(iPr)₂]₂,Si(OnPr)₂[CH₂—SiH(nPr)₂]₂, Si(OnPr)₂[CH₂—SiH(nBu)₂]₂,Si(OnPr)₂[CH₂—SiH(OtBu)₂]₂, Si(OnPr)₂[CH₂—SiH(iBu)₂]₂,Si(OnPr)₂[CH₂—SiH(SiMe₃)₂]₂, Si(OnBu)₂[CH₂—SiHMe₂]₂,Si(OnBu)₂[CH₂—SiHEt₂]₂, Si(OnBu)₂[CH₂—SiH(iPr)₂]₂,Si(OnBu)₂[CH₂—SiH(nPr)₂]₂, Si(OnBu)₂[CH₂—SiH(nBu)₂]₂,Si(OnBu)₂[CH₂—SiH(OtBu)₂]₂, Si(OnBu)₂[CH₂—SiH(iBu)₂]₂,Si(OnBu)₂[CH₂—SiH(SiMe₃)₂]₂, Si(OiBu)₂[CH₂—SiHMe₂]2,Si(OiBu)₂[CH₂—SiHEt₂]₂, Si(OiBu)₂[CH₂—SiH(iPr)₂]₂,Si(OiBu)₂[CH₂—SiH(nPr)₂]₂, Si(OiBu)₂[CH₂—SiH(nBu)₂]₂,Si(OiBu)₂[CH₂—SiH(OtBu)₂]₂, Si(OiBu)₂[CH₂—SiH(iBu)₂]₂,Si(OiBu)₂[CH₂—SiH(SiMe₃)₂]₂, Si(OtBu)₂[CH₂—SiHMe₂]₂,Si(OtBu)₂[CH₂—SiHEt₂]₂, Si(OtBu)₂[CH₂—SiH(iPr)₂]₂,Si(OtBu)₂[CH₂—SiH(nPr)₂]₂, Si(OtBu)₂[CH₂—SiH(nBu)₂]₂,Si(OtBu)₂[CH₂—SiH(OtBu)₂]₂, Si(OtBu)₂[CH₂—SiH(iBu)₂]₂,Si(OtBu)₂[CH₂—SiH(SiMe₃)₂]₂, Si(OSiMe₃)₂[CH₂—SiHMe₂]₂,Si(OSiMe₃)₂[CH₂—SiHEt₂]₂, Si(OSiMe₃)₂[CH₂—SiH(iPr)₂]₂,Si(OSiMe₃)₂[CH₂—SiH(nPr)₂]₂, Si(OSiMe₃)₂[CH₂—SiH(nBu)₂]₂,Si(OSiMe₃)₂[CH₂—SiH(OtBu)₂]₂, Si(OSiMe₃)₂[CH₂—SiH(iBu)₂]₂, andSi(OSiMe₃)₂[CH₂—SiH(SiMe₃)₂]₂.

Exemplary compounds wherein a=2, b=2, c=0, x=0, y=0, and z=3 includeSi(OMe)₂[CH₂—SiMe₃]₂, Si(OMe)₂[CH₂—SiEt₃]₂, Si(OMe)₂[CH₂—Si(iPr)₃]₂,Si(OMe)₂[CH₂—Si(nPr)₃]₂, Si(OMe)₂[CH₂—Si(nBu)₃]₂,Si(OMe)₂[CH₂—Si(OtBu)₃]₂, Si(OMe)₂[CH₂—Si(iBu)₃]₂,Si(OMe)₂[CH₂—Si(SiMe₃)₃]₂, Si(OEt)₂[CH₂—SiMe₃]₂, Si(OEt)₂[CH₂—SiEt₃]₂,Si(OEt)₂[CH₂—Si(iPr)₃]₂, Si(OEt)₂[CH₂—SiH(nPr)₃]₂,Si(OEt)₂[CH₂—Si(nBu)₃]₂, Si(OEt)₂[CH₂—Si(OtBu)₃]₂,Si(OEt)₂[CH₂—Si(iBu)₃]₂, Si(OEt)₂[CH₂—Si(SiMe₃)₃]₂,Si(OiPr)₂[CH₂—SiMe₃]₂, Si(OiPr)₂[CH₂—SiEt₃]₂, Si(OiPr)₂[CH₂—Si(iPr)₃]₂,Si(OiPr)₂[CH₂—Si(nPr)₃]₂, Si(OiPr)₂[CH₂—Si(nBu)₃]₂,Si(OiPr)₂[CH₂—Si(OtBu)₃]₂, Si(OiPr)₂[CH₂—Si(iBu)₃]₂,Si(OiPr)₂[CH₂—Si(SiMe₃)₃]₂, Si(OnPr)₂[CH₂—SiMe₃]₂,Si(OnPr)₂[CH₂—SiEt₃]₂, Si(OnPr)₂[CH₂—Si(iPr)₃]₂,Si(OnPr)₂[CH₂—Si(nPr)₃]₂, Si(OnPr)₂[CH₂—Si(nBu)₃]₂,Si(OnPr)₂[CH₂—Si(OtBu)₃]₂, Si(OnPr)₂[CH₂—Si(iBu)₃]₂,Si(OnPr)₂[CH₂—Si(SiMe₃)₃]₂, Si(OnBu)₂[CH₂—SiMe₃]₂,Si(OnBu)₂[CH₂—SiEt₃]₂, Si(OnBu)₂[CH₂—Si(iPr)₃]₂,Si(OnBu)₂[CH₂—Si(nPr)₃]₂, Si(OiBu)₂[CH₂—Si(OtBu)₃]₂,Si(OnBu)₂[CH₂—Si(OtBu)₃]₂, Si(OnBu)₂[CH₂—Si(iBu)₃]₂,Si(OnBu)₂[CH₂—Si(SiMe₃)₃]₂, Si(OiBu)₂[CH₂—SiMe₃]₂,Si(OiBu)₂[CH₂—SiEt₃]₂, Si(OiBu)₂[CH₂—Si(iPr)₃]₂,Si(OiBu)₂[CH₂—Si(nPr)₃]₂, Si(OiBu)₂[CH₂—Si(nBu)₃]₂,Si(OiBu)₂[CH₂—SiH(OtBu)₂]₂, Si(OiBu)₂[CH₂—Si(iBu)₃]₂,Si(OiBu)₂[CH₂—Si(SiMe₃)₃]₂, Si(OtBu)₂[CH₂—SiMe₃]₂,Si(OtBu)₂[CH₂—SiEt₃]₂, Si(OtBu)₂[CH₂—Si(iPr)₃]₂,Si(OtBu)₂[CH₂—Si(nPr)₃]₂, Si(OtBu)₂[CH₂—Si(nBu)₃]₂,Si(OtBu)₂[CH₂—Si(OtBu)₃]₂, Si(OtBu)₂[CH₂—Si(iBu)₃]₂,Si(OtBu)₂[CH₂—Si(SiMe₃)₃]₂, Si(OSiMe₃)₂[CH₂—SiMe₃]₂,Si(OSiMe₃)₂[CH₂—SiEt₃]₂, Si(OSiMe₃)₂[CH₂—Si(iPr)₃]₂,Si(OSiMe₃)₂[CH₂—Si(nPr)₃]₂, Si(OSiMe₃)₂[CH₂—Si(nBu)₃]₂,Si(OSiMe₃)₂[CH₂—Si(OtBu)₃]₂, Si(OSiMe₃)₂[CH₂—Si(iBu)₃]₂, andSi(OSiMe₃)₂[CH₂—Si(SiMe₃)₃]₂.

In some embodiments, y=1 and b=0 to produceSi(H)_(c)[CH₂—Si(OR′)_(x)HR_(2-x)]_(a), wherein a=1 to 3; c=0 to 2;a+c=4; x=0 to 2; each R is independently a C1 to C5 linear or branchedalkyl group or a trimethylsilyl group; and each R′ is independently a C1to C5 linear or branched alkyl group.

Exemplary compounds wherein y=1, b=0, a=3, c=1, x=2, and z=0 includeSiH[CH₂—SiH(OMe)₂]₃, SiH[CH₂—SiH(OEt)₂]₃, SiH[CH₂—SiH(OiPr)₂]₃,SiH[CH₂—SiH(OnPr)₂]₃, SiH[CH₂—SiH(OnBu)₂]₃, SiH[CH₂—SiH(OtBu)₂]₃, andSiH[CH₂—SiH(OiBu)₂]₃.

Exemplary compounds wherein y=1, b=0, a=3, c=1, x=0, and z=2 includeSiH[CH₂—SiH(Me)₂]₃, SiH[CH₂—SiH(Et)₂]₃, SiH[CH₂—SiH(iPr)₂]₃,SiH[CH₂—SiH(nPr)₂]₃, SiH[CH₂—SiH(nBu)₂]₃, SiH[CH₂—SiH(tBu)₂]₃,SiH[CH₂—SiH(iBu)₂]₃, and SiH[CH₂—SiH(SiMe₃)₂]₃.

Exemplary compounds wherein y=1, b=0, a=3, c=1, x=1, and z=1 includeSiH[CH₂—SiH(Me)(OMe)]₃, SiH[CH₂—SiH(Me)(OEt)]₃, SiH[CH₂—SiH(Me)(OiPr)]₃,SiH[CH₂—SiH(Me)(OnPr)]₃, SiH[CH₂—SiH(Me)(OnBu)]₃,SiH[CH₂—SiH(Me)(OtBu)]₃, SiH[CH₂—SiH(Me)(OiBu)]₃,SiH[CH₂—SiH(Et)(OMe)]₃, SiH[CH₂—SiH(Et)(OEt)]₃, SiH[CH₂—SiH(Et)(OiPr)]₃,SiH[CH₂—SiH(Et)(OnPr)]₃, SiH[CH₂—SiH(Et)(OnBu)]₃,SiH[CH₂—SiH(Et)(OtBu)]₃, SiH[CH₂—SiH(Et)(OiBu)]₃,SiH[CH₂—SiH(Pr)(OMe)]₃, SiH[CH₂—SiH(iPr)(OEt)]₃,SiH[CH₂—SiH(iPr)(OiPr)]₃, SiH[CH₂—SiH(iPr)(OnPr)]₃,SiH[CH₂—SiH(iPr)(OnBu)]₃, SiH[CH₂—SiH(iPr)(OtBu)]₃,SiH[CH₂—SiH(iPr)(OiBu)]₃, SiH[CH₂—SiH(nPr)(OMe)]₃,SiH[CH₂—SiH(nPr)(OEt)]₃, SiH[CH₂—SiH(nPr)(OiPr)]₃,SiH[CH₂—SiH(nPr)(OnPr)]₃, SiH[CH₂—SiH(nPr)(OnBu)]₃,SiH[CH₂—SiH(nPr)(OtBu)]₃, SiH[CH₂—SiH(nPr)(OiBu)]₃,SiH[CH₂—SiH(nBu)(OMe)]₃, SiH[CH₂—SiH(nBu)(OEt)]₃,SiH[CH₂—SiH(nBu)(OiPr)]₃, SiH[CH₂—SiH(nBu)(OnPr)]₃,SiH[CH₂—SiH(nBu)(OnBu)]₃, SiH[CH₂—SiH(nBu)(OtBu)]₃,SiH[CH₂—SiH(nBu)(OiBu)]₃, SiH[CH₂—SiH(tBu)(OMe)]₃,SiH[CH₂—SiH(tBu)(OEt)]₃, SiH[CH₂—SiH(tBu)(OiPr)]₃,SiH[CH₂—SiH(tBu)(OnPr)]₃, SiH[CH₂—SiH(tBu)(OnBu)]₃,SiH[CH₂—SiH(tBu)(OtBu)]₃, SiH[CH₂—SiH(tBu)(OiBu)]₃,SiH[CH₂—SiH(iBu)(OMe)]₃, SiH[CH₂—SiH(iBu)(OEt)]₃,SiH[CH₂—SiH(iBu)(OiPr)]₃, SiH[CH₂—SiH(iBu)(OnPr)]₃,SiH[CH₂—SiH(iBu)(OnBu)]₃, SiH[CH₂—SiH(iBu)(OtBu)]₃,SiH[CH₂—SiH(iBu)(OiBu)]₃, SiH[CH₂—SiH(SiMe₃)(OMe)]₃,SiH[CH₂—SiH(SiMe₃)(OEt)]₃, SiH[CH₂—SiH(SiMe₃)(OiPr)]₃,SiH[CH₂—SiH(SiMe₃)(OnPr)]₃, SiH[CH₂—SiH(SiMe₃)(OnBu)]₃,SiH[CH₂—SiH(SiMe₃)(OtBu)]₃, and SiH[CH₂—SiH(SiMe₃)(OiBu)]₃.

Exemplary compounds wherein y=1, b=0, a=2, c=2, x=2, and z=0 includeSiH₂[CH₂—SiH(OMe)₂]₂, SiH₂[CH₂—SiH(OEt)₂]₂, SiH₂[CH₂—SiH(OiPr)₂]₂,SiH₂[CH₂—SiH(OnPr)₂]₂, SiH₂[CH₂—SiH(OnBu)₂]₂, SiH₂[CH₂—SiH(OtBu)₂]₂, andSiH₂[CH₂—SiH(OiBu)₂]₂.

Exemplary compounds wherein y=1, b=0, a=2, c=2, x=0, and z=2 includeSiH₂[CH₂—SiH(Me)₂]₂, SiH₂[CH₂—SiH(Et)₂]₂, SiH₂[CH₂—SiH(iPr)₂]₂,SiH₂[CH₂—SiH(nPr)₂]₂, SiH₂[CH₂—SiH(nBu)₂]₂, SiH₂[CH₂—SiH(tBu)₂]₂,SiH₂[CH₂—SiH(iBu)₂]₂, and SiH₂[CH₂—SiH(SiMe₃)₂]₂.

Exemplary compounds wherein y=1, b=0, a=2, c=2, x=1, and z=1 includeSiH₂[CH₂—SiH(Me)(OMe)]₂, SiH₂[CH₂—SiH(Me)(OEt)]₂,SiH₂[CH₂—SiH(Me)(OiPr)]₂, SiH₂[CH₂—SiH(Me)(OnPr)]₂,SiH₂[CH₂—SiH(Me)(OnBu)]₂, SiH₂[CH₂—SiH(Me)(OiBu)]₂,SiH₂[CH₂—SiH(Me)(OtBu)]₂, SiH₂[CH₂—SiH(Et)(OMe)]₂,SiH₂[CH₂—SiH(Et)(OEt)]₂, SiH₂[CH₂—SiH(Et)(OiPr)]₂,SiH₂[CH₂—SiH(Et)(OnPr)]₂, SiH₂[CH₂—SiH(Et)(OnBu)]₂,SiH₂[CH₂—SiH(Et)(OtBu)]₂, SiH₂[CH₂—SiH(Et)(OiBu)]₂,SiH₂[CH₂—SiH(iPr)(OMe)]₂, SiH₂[CH₂—SiH(iPr)(OEt)]₂,SiH₂[CH₂—SiH(iPr)(OiPr)]₂, SiH₂[CH₂—SiH(iPr)(OnPr)]₂,SiH₂[CH₂—SiH(iPr)(OnBu)]₂, SiH₂[CH₂—SiH(iPr)(OtBu)]₂,SiH₂[CH₂—SiH(iPr)(OiBu)]₂, SiH₂[CH₂—SiH(nPr)(OMe)]₂,SiH₂[CH₂—SiH(nPr)(OEt)]₂, SiH₂[CH₂—SiH(nPr)(OnPr)]₂,SiH₂[CH₂—SiH(nPr)(OiPr)]₂, SiH₂[CH₂—SiH(nPr)(OnBu)]₂,SiH₂[CH₂—SiH(nPr)(OtBu)]₂, SiH₂[CH₂—SiH(nPr)(OiBu)]₂,SiH₂[CH₂—SiH(nBu)(OMe)]₂, SiH₂[CH₂—SiH(nBu)(OEt)]₂,SiH₂[CH₂—SiH(nBu)(OnPr)]₂, SiH₂[CH₂—SiH(nBu)(OiPr)]₂,SiH₂[CH₂—SiH(nBu)(OnBu)]₂, SiH₂[CH₂—SiH(nBu)(OtBu)]₂,SiH₂[CH₂—SiH(nBu)(OiBu)]₂, SiH₂[CH₂—SiH(tBu)(OMe)]₂,SiH₂[CH₂—SiH(tBu)(OEt)]₂, SiH₂[CH₂—SiH(tBu)(OnPr)]₂,SiH₂[CH₂—SiH(tBu)(OiPr)]₂, SiH₂[CH₂—SiH(tBu)(OnBu)]₂,SiH₂[CH₂—SiH(tBu)(OtBu)]₂, SiH₂[CH₂—SiH(tBu)(OiBu)]₂,SiH₂[CH₂—SiH(iBu)(OMe)]₂, SiH₂[CH₂—SiH(iBu)(OEt)]₂,SiH₂[CH₂—SiH(iBu)(OnPr)]₂, SiH₂[CH₂—SiH(iBu)(OiPr)]₂,SiH₂[CH₂—SiH(iBu)(OnBu)]₂, SiH₂[CH₂—SiH(iBu)(OtBu)]₂,SiH₂[CH₂—SiH(iBu)(OiBu)]₂, SiH₂[CH₂—SiH(SiMe₃)(OMe)]₂,SiH₂[CH₂—SiH(SiMe₃)(OEt)]₂, SiH₂[CH₂—SiH(SiMe₃)(OnPr)]₂,SiH₂[CH₂—SiH(SiMe₃)(OiPr)]₂, SiH₂[CH₂—SiH(SiMe₃)(OnBu)]₂,SiH₂[CH₂—SiH(SiMe₃)(OtBu)]₂, and SiH₂[CH₂—SiH(SiMe₃)(OiBu)]₂.

In some embodiments, z=0 and c=2 to produceSi(OR)_(2-a)H₂[CH₂—Si(OR)_(3-y)H_(y)]_(a), wherein a=1 to 2; y=0 to 1;each R is independently a C1 to C5 linear or branched alkyl group or atrimethylsilyl group; and each R′ is independently a C1 to C5 linear orbranched alkyl group.

Exemplary compounds wherein z=0, c=2, a=2, and y=1 includeSiH₂[CH₂—SiH(OMe)₂]₂, SiH₂[CH₂—SiH(OEt)₂]₂, SiH₂[CH₂—SiH(OiPr)₂]₂,SiH₂[CH₂—SiH(OnPr)₂]₂, SiH₂[CH₂—SiH(OnBu)₂]₂, SiH₂[CH₂—SiH(OtBu)₂]₂,SiH₂[CH₂—SiH(OiBu)₂]₂,

Exemplary compounds wherein z=0, c=2, a=2, and y=0 includeSiH₂[CH₂—Si(OMe)₃]₂, SiH₂[CH₂—Si(OEt)₃]₂, SiH₂[CH₂—Si(OiPr)₃]₂,SiH₂[CH₂—Si(OnPr)₃]₂, SiH₂[CH₂—Si(OnBu)₃]₂, SiH₂[CH₂—Si(OtBu)₃]₂,SiH₂[CH₂—Si(OiBu)₃]₂,

Exemplary compounds wherein z=0, c=2, a=1, and y=1 includeSi(OMe)H₂[CH₂—SiH(OMe)₂], Si(OMe)H₂[CH₂—SiH(OEt)₂],Si(OMe)H₂[CH₂—SiH(OiPr)₂], Si(OMe)H₂[CH₂—SiH(OnPr)₂],Si(OMe)H₂[CH₂—SiH(OnBu)₂], Si(OMe)H₂[CH₂—SiH(OtBu)₂],Si(OMe)H₂[CH₂—SiH(OiBu)₂], Si(OEt)H₂[CH₂—SiH(OMe)₂],Si(OEt)H₂[CH₂—SiH(OEt)₂], Si(OEt)H₂[CH₂—SiH(OiPr)₂],Si(OEt)H₂[CH₂—SiH(OnPr)₂], Si(OEt)H₂[CH₂—SiH(OnBu)₂],Si(OEt)H₂[CH₂—SiH(OtBu)₂], Si(OEt)H₂[CH₂—SiH(OiBu)₂],Si(OiPr)H₂[CH₂—SiH(OMe)₂], Si(OiPr)H₂[CH₂—SiH(OEt)₂],Si(OiPr)H₂[CH₂—SiH(OiPr)₂], Si(OiPr)H₂[CH₂—SiH(OnPr)₂],Si(OiPr)H₂[CH₂—SiH(OnBu)₂], Si(OiPr)H₂[CH₂—SiH(OtBu)₂],Si(OiPr)H₂[CH₂—SiH(OiBu)₂], Si(OnPr)H₂[CH₂—SiH(OMe)₂],Si(OnPr)H₂[CH₂—SiH(OEt)₂], Si(OnPr)H₂[CH₂—SiH(OiPr)₂],Si(OnPr)H₂[CH₂—SiH(OnPr)₂], Si(OnPr)H₂[CH₂—SiH(OnBu)₂],Si(OnPr)H₂[CH₂—SiH(OtBu)₂], Si(OnPr)H₂[CH₂—SiH(OiBu)₂],Si(OnBu)H₂[CH₂—SiH(OMe)₂], Si(OnBu)H₂[CH₂—SiH(OEt)₂],Si(OnBu)H₂[CH₂—SiH(OiPr)₂], Si(OnBu)H₂[CH₂—SiH(OnPr)₂],Si(OnBu)H₂[CH₂—SiH(OnBu)₂], Si(OnBu)H₂[CH₂—SiH(OtBu)₂],Si(OnBu)H₂[CH₂—SiH(OiBu)₂], Si(OtBu)H₂[CH₂—SiH(OMe)₂],Si(OtBu)H₂[CH₂—SiH(OEt)₂], Si(OtBu)H₂[CH₂—SiH(OiPr)₂],Si(OtBu)H₂[CH₂—SiH(OnPr)₂], Si(OtBu)H₂[CH₂—SiH(OnBu)₂],Si(OtBu)H₂[CH₂—SiH(OtBu)₂], Si(OtBu)H₂[CH₂—SiH(OiBu)₂],Si(OiBu)H₂[CH₂—SiH(OMe)₂], Si(OiBu)H₂[CH₂—SiH(OEt)₂],Si(OiBu)H₂[CH₂—SiH(OiPr)₂], Si(OiBu)H₂[CH₂—SiH(OnPr)₂],Si(OiBu)H₂[CH₂—SiH(OnBu)₂], Si(OiBu)H₂[CH₂—SiH(OtBu)₂],Si(OiBu)H₂[CH₂—SiH(OiBu)₂], Si(OSiMe₃)H₂[CH₂—SiH(OMe)₂],Si(OSiMe₃)H₂[CH₂—SiH(OEt)₂], Si(OSiMe₃)H₂[CH₂—SiH(OiPr)₂],Si(OSiMe₃)H₂[CH₂—SiH(OnPr)₂], Si(OSiMe₃)H₂[CH₂—SiH(OnBu)₂],Si(OSiMe₃)H₂[CH₂—SiH(OtBu)₂], Si(OSiMe₃)H₂[CH₂—SiH(OiBu)₂].

Exemplary compounds wherein z=0, c=2, a=1, and y=0 includeSi(OMe)H₂[CH₂—Si(OMe)₃], Si(OMe)H₂[CH₂—Si(OEt)₃],Si(OMe)H₂[CH₂—Si(OiPr)₃], Si(OMe)H₂[CH₂—Si(OnPr)₃],Si(OMe)H₂[CH₂—Si(OnBu)₃], Si(OMe)H₂[CH₂—Si(OtBu)₃],Si(OMe)H₂[CH₂—Si(OiBu)₃], Si(OEt)H₂[CH₂—Si(OMe)₃],Si(OEt)H₂[CH₂—Si(OEt)₃], Si(OEt)H₂[CH₂—Si(OiPr)₃],Si(OEt)H₂[CH₂—Si(OnPr)₃], Si(OEt)H₂[CH₂—Si(OnBu)₃],Si(OEt)H₂[CH₂—Si(OtBu)₃], Si(OEt)H₂[CH₂—Si(OiBu)₃],Si(OiPr)H₂[CH₂—Si(OMe)₃], Si(OiPr)H₂[CH₂—Si(OEt)₃],Si(OiPr)H₂[CH₂—Si(OiPr)₃], Si(OiPr)H₂[CH₂—Si(OnPr)₃],Si(OiPr)H₂[CH₂—Si(OnBu)₃], Si(OiPr)H₂[CH₂—Si(OtBu)₃],Si(OiPr)H₂[CH₂—Si(OiBu)₃], Si(OnPr)H₂[CH₂—Si(OMe)₃],Si(OnPr)H₂[CH₂—Si(OEt)₃], Si(OnPr)H₂[CH₂—Si(OiPr)₃],Si(OnPr)H₂[CH₂—Si(OnPr)₃], Si(OnPr)H₂[CH₂—Si(OnBu)₃],Si(OnPr)H₂[CH₂—Si(OtBu)₃], Si(OnPr)H₂[CH₂—Si(OiBu)₃],Si(OnBu)H₂[CH₂—Si(OMe)₃], Si(OnBu)H₂[CH₂—Si(OEt)₃],Si(OnBu)H₂[CH₂—Si(OiPr)₃], Si(OnBu)H₂[CH₂—Si(OnPr)₃],Si(OnBu)H₂[CH₂—Si(OnBu)₃], Si(OnBu)H₂[CH₂—Si(OtBu)₃],Si(OnBu)H₂[CH₂—Si(OiBu)₃], Si(OtBu)H₂[CH₂—Si(OMe)₃],Si(OtBu)H₂[CH₂—Si(OEt)₃], Si(OtBu)H₂[CH₂—Si(OiPr)₃],Si(OtBu)H₂[CH₂—Si(OnPr)₃], Si(OtBu)H₂[CH₂—Si(OnBu)₃],Si(OtBu)H₂[CH₂—Si(OtBu)₃], Si(OtBu)H₂[CH₂—Si(OiBu)₃],Si(OiBu)H₂[CH₂—Si(OMe)₃], Si(OiBu)H₂[CH₂—Si(OEt)₃],Si(OiBu)H₂[CH₂—Si(OiPr)₃], Si(OiBu)H₂[CH₂—Si(OnPr)₃],Si(OiBu)H₂[CH₂—Si(OnBu)₃], Si(OiBu)H₂[CH₂—Si(OtBu)₃],Si(OiBu)H₂[CH₂—Si(OiBu)₃], Si(OSiMe₃)H₂[CH₂—Si(OMe)₃],Si(OSiMe₃)H₂[CH₂—Si(OEt)₃], Si(OSiMe₃)H₂[CH₂—Si(OiPr)₃],Si(OSiMe₃)H₂[CH₂—Si(OnPr)₃], Si(OSiMe₃)H₂[CH₂—Si(OnBu)₃],Si(OSiMe₃)H₂[CH₂—Si(OtBu)₃], and Si(OSiMe₃)H₂[CH₂—Si(OiBu)₃].

In some embodiments, b=0 and c=2 to produceSiH₂[CH₂—Si(OR)_(x)H_(y)R_(z)]₂, wherein x=0 to 3; y=0-1; z=0-3; each Ris independently a C1 to C5 linear or branched alkyl group or atrimethylsilyl group; and each R′ is independently a C1 to C5 linear orbranched alkyl group.

Exemplary compounds wherein b=0, c=2, x=3, y=0, and z=0 includeSiH₂[CH₂—Si(OMe)₃]₂, SiH₂[CH₂—Si(OEt)₃]₂, SiH₂[CH₂—Si(OiPr)₃]₂,SiH₂[CH₂—Si(OnPr)₃]₂, SiH₂[CH₂—Si(OnBu)₃]₂, SiH₂[CH₂—Si(OtBu)₃]₂, andSiH₂[CH₂—Si(OiBu)₃]₂.

Exemplary compounds wherein b=0, c=2, x=0, y=0, and z=3 includeSiH₂[CH₂—Si(Me)₃]₂, SiH₂[CH₂—Si(Et)₃]₂, SiH₂[CH₂—Si(iPr)₃]₂,SiH₂[CH₂—Si(nPr)₃]₂, SiH₂[CH₂—Si(nBu)₃]₂, SiH₂[CH₂—Si(tBu)₃]₂,SiH₂[CH₂—Si(iBu)₃]₂, and SiH₂[CH₂—Si(SiMe₃)₃]₂.

Exemplary compounds wherein b=0, c=2, x=2, y=1, and z=0 includeSiH₂[CH₂—SiH(OMe)₂]₂, SiH₂[CH₂—SiH(OEt)₂]₂, SiH₂[CH₂—SiH(OiPr)₂]₂,SiH₂[CH₂—SiH(OnPr)₂]₂, SiH₂[CH₂—SiH(OnBu)₂]₂, SiH₂[CH₂—SiH(OtBu)₂]₂,SiH₂[CH₂—SiH(OiBu)₂]₂.

Exemplary compounds wherein b=0, c=2, x=0, y=1, and z=2 includeSiH₂[CH₂—SiH(Me)₂]₂, SiH₂[CH₂—SiH(Et)₂]₂, SiH₂[CH₂—SiH(iPr)₂]₂,SiH₂[CH₂—SiH(nPr)₂]₂, SiH₂[CH₂—SiH(nBu)₂]₂, SiH₂[CH₂—SiH(tBu)₂]₂,SiH₂[CH₂—SiH(iBu)₂]₂, SiH₂[CH₂—SiH(SiMe₃)₂]₂.

Exemplary compounds wherein b=0, c=2, x=1, y=1, and z=1 includeSiH₂[CH₂—SiH(Me)(OMe)]₂, SiH₂[CH₂—SiH(Me)(OEt)]₂,SiH₂[CH₂—SiH(Me)(OiPr)]₂, SiH₂[CH₂—SiH(Me)(OnPr)]₂,SiH₂[CH₂—SiH(Me)(OnBu)]₂, SiH₂[CH₂—SiH(Me)(OiBu)]₂,SiH₂[CH₂—SiH(Me)(OtBu)]₂, SiH₂[CH₂—SiH(Et)(OMe)]₂,SiH₂[CH₂—SiH(Et)(OEt)]₂, SiH₂[CH₂—SiH(Et)(OiPr)]₂,SiH₂[CH₂—SiH(Et)(OnPr)]₂, SiH₂[CH₂—SiH(Et)(OnBu)]₂,SiH₂[CH₂—SiH(Et)(OtBu)]₂, SiH₂[CH₂—SiH(Et)(OiBu)]₂,SiH₂[CH₂—SiH(iPr)(OMe)]₂, SiH₂[CH₂—SiH(iPr)(OEt)]₂,SiH₂[CH₂—SiH(iPr)(OiPr)]₂, SiH₂[CH₂—SiH(iPr)(OnPr)]₂,SiH₂[CH₂—SiH(iPr)(OnBu)]₂, SiH₂[CH₂—SiH(iPr)(OtBu)]₂,SiH₂[CH₂—SiH(iPr)(OiBu)]₂, SiH₂[CH₂—SiH(nPr)(OMe)]₂,SiH₂[CH₂—SiH(nPr)(OEt)]₂, SiH₂[CH₂—SiH(nPr)(OnPr)]₂,SiH₂[CH₂—SiH(nPr)(OiPr)]₂, SiH₂[CH₂—SiH(nPr)(OnBu)]₂,SiH₂[CH₂—SiH(nPr)(OtBu)]₂, SiH₂[CH₂—SiH(nPr)(OiBu)]₂,SiH₂[CH₂—SiH(nBu)(OMe)]₂, SiH₂[CH₂—SiH(nBu)(OEt)]₂,SiH₂[CH₂—SiH(nBu)(OnPr)]₂, SiH₂[CH₂—SiH(nBu)(OiPr)]₂,SiH₂[CH₂—SiH(nBu)(OnBu)]₂, SiH₂[CH₂—SiH(nBu)(OtBu)]₂,SiH₂[CH₂—SiH(nBu)(OiBu)]₂, SiH₂[CH₂—SiH(tBu)(OMe)]₂,SiH₂[CH₂—SiH(tBu)(OEt)]₂, SiH₂[CH₂—SiH(tBu)(OnPr)]₂,SiH₂[CH₂—SiH(tBu)(OiPr)]₂, SiH₂[CH₂—SiH(tBu)(OnBu)]₂,SiH₂[CH₂—SiH(tBu)(OtBu)]₂, SiH₂[CH₂—SiH(tBu)(OiBu)]₂,SiH₂[CH₂—SiH(iBu)(OMe)]₂, SiH₂[CH₂—SiH(iBu)(OEt)]₂,SiH₂[CH₂—SiH(iBu)(OnPr)]₂, SiH₂[CH₂—SiH(iBu)(OiPr)]₂,SiH₂[CH₂—SiH(iBu)(OnBu)]₂, SiH₂[CH₂—SiH(iBu)(OtBu)]₂,SiH₂[CH₂—SiH(iBu)(OiBu)]₂, SiH₂[CH₂—SiH(SiMe₃)(OMe)]₂,SiH₂[CH₂—SiH(SiMe₃)(OEt)]₂, SiH₂[CH₂—SiH(SiMe₃)(OnPr)]₂,SiH₂[CH₂—SiH(SiMe₃)(OiPr)]₂, SiH₂[CH₂—SiH(SiMe₃)(OnBu)]₂,SiH₂[CH₂—SiH(SiMe₃)(OtBu)]₂, and SiH₂[CH₂—SiH(SiMe₃)(OiBu)]₂.

Exemplary compounds wherein b=0, c=2, x=1, y=0, and z=2 includeSiH₂[CH₂—Si(Me)₂(OMe)]₂, SiH₂[CH₂—Si(Me)₂(OEt)]₂,SiH₂[CH₂—Si(Me)₂(OiPr)]₂, SiH₂[CH₂—Si(Me)₂(OnPr)]₂,SiH₂[CH₂—Si(Me)₂(OnBu)]₂, SiH₂[CH₂—Si(Me)₂(OiBu)]₂,SiH₂[CH₂—Si(Me)₂(OtBu)]₂, SiH₂[CH₂—Si(Et)₂(OMe)]₂,SiH₂[CH₂—Si(Et)₂(OEt)]₂, SiH₂[CH₂—Si(Et)₂(OiPr)]₂,SiH₂[CH₂—Si(Et)₂(OnPr)]₂, SiH₂[CH₂—Si(Et)₂(OnBu)]₂,SiH₂[CH₂—Si(Et)₂(OtBu)]₂, SiH₂[CH₂—Si(Et)₂(OiBu)]₂,SiH₂[CH₂—Si(iPr)₂(OMe)]₂, SiH₂[CH₂—Si(iPr)₂(OEt)]₂,SiH₂[CH₂—Si(iPr)₂(OiPr)]₂, SiH₂[CH₂—Si(iPr)₂(OnPr)]₂,SiH₂[CH₂—Si(iPr)₂(OnBu)]₂, SiH[CH₂—Si(iPr)₂(OtBu)]₂,SiH₂[CH₂—Si(iPr)₂(OiBu)]₂, SiH₂[CH₂—Si(nPr)₂(OMe)]₂,SiH₂[CH₂—Si(nPr)₂(OEt)]₂, SiH₂[CH₂—Si(nPr)₂(OnPr)]₂,SiH₂[CH₂—Si(nPr)₂(OiPr)]₂, SiH₂[CH₂—Si(nPr)₂(OnBu)]₂,SiH₂[CH₂—Si(nPr)₂(OtBu)]₂, SiH₂[CH₂—Si(nPr)₂(OiBu)]₂,SiH₂[CH₂—Si(nBu)₂(OMe)]₂, SiH₂[CH₂—Si(nBu)₂(OEt)]₂,SiH₂[CH₂—Si(nBu)₂(OnPr)]₂, SiH₂[CH₂—Si(nBu)₂(OiPr)]₂,SiH₂[CH₂—Si(nBu)₂(OnBu)]₂, SiH₂[CH₂—Si(nBu)₂(OtBu)]₂,SiH₂[CH₂—Si(nBu)₂(OiBu)]₂, SiH₂[CH₂—Si(tBu)₂(OMe)]₂,SiH₂[CH₂—Si(tBu)₂(OEt)]₂, SiH₂[CH₂—Si(tBu)₂(OnPr)]₂,SiH₂[CH₂—Si(tBu)₂(OiPr)]₂, SiH₂[CH₂—Si(tBu)₂(OnBu)]₂,SiH₂[CH₂—Si(tBu)₂(OtBu)]₂, SiH₂[CH₂—Si(tBu)₂(OiBu)]₂,SiH₂[CH₂—Si(iBu)₂(OMe)]₂, SiH₂[CH₂—Si(iBu)₂(OEt)]₂,SiH₂[CH₂—Si(iBu)₂(OnPr)]₂, SiH₂[CH₂—Si(iBu)₂(OiPr)]₂,SiH₂[CH₂—Si(iBu)₂(OnBu)]₂, SiH₂[CH₂—Si(iBu)₂(OtBu)]₂,SiH₂[CH₂—Si(iBu)₂(OiBu)]₂, SiH₂[CH₂—Si(SiMe₃)₂(OMe)]₂,SiH₂[CH₂—Si(SiMe₃)₂(OEt)]₂, SiH₂[CH₂—Si(SiMe₃)₂(OnPr)]₂,SiH₂[CH₂—Si(SiMe₃)₂(OiPr)]₂, SiH₂[CH₂—Si(SiMe₃)₂(OnBu)]₂,SiH₂[CH₂—Si(SiMe₃)₂(OtBu)]₂, and SiH₂[CH₂—Si(SiMe₃)₂(OiBu)]₂.

Exemplary compounds wherein b=0, c=2, x=2, y=0, and z=1 includeSiH₂[CH₂—Si(Me)(OMe)₂]₂, SiH₂[CH₂—Si(Me)(OEt)₂]₂,SiH₂[CH₂—Si(Me)(OiPr)₂]₂, SiH₂[CH₂—Si(Me)(OnPr)₂]₂,SiH₂[CH₂—Si(Me)(OnBu)₂]₂, SiH₂[CH₂—Si(Me)(OiBu)₂]₂,SiH₂[CH₂—Si(Me)(OtBu)₂]₂, SiH₂[CH₂—Si(Et)(OMe)₂]₂,SiH₂[CH₂—Si(Et)(OEt)₂]₂, SiH₂[CH₂—Si(Et)(OiPr)₂]₂,SiH₂[CH₂—Si(Et)(OnPr)₂]₂, SiH₂[CH₂—Si(Et)(OnBu)₂]₂,SiH₂[CH₂—Si(Et)(OtBu)₂]₂, SiH₂[CH₂—Si(Et)(OiBu)₂]₂,SiH₂[CH₂—Si(iPr)(OMe)₂]₂, SiH₂[CH₂—Si(iPr)(OEt)₂]₂,SiH₂[CH₂—Si(iPr)(OiPr)₂]₂, SiH₂[CH₂—Si(iPr)(OnPr)₂]₂,SiH₂[CH₂—Si(iPr)(OnBu)₂]₂, SiH₂[CH₂—Si(iPr)(OtBu)₂]₂,SiH₂[CH₂—Si(iPr)(OiBu)₂]₂, SiH₂[CH₂—Si(nPr)(OMe)₂]₂,SiH₂[CH₂—Si(nPr)(OEt)₂]₂, SiH₂[CH₂—Si(nPr)(OnPr)₂]₂,SiH₂[CH₂—Si(nPr)(OiPr)₂]₂, SiH₂[CH₂—Si(nPr)(OnBu)₂]₂,SiH₂[CH₂—Si(nPr)(OtBu)₂]₂, SiH₂[CH₂—Si(nPr)(OiBu)₂]₂,SiH₂[CH₂—Si(nBu)(OMe)₂]₂, SiH₂[CH₂—Si(nBu)(OEt)₂]₂,SiH₂[CH₂—Si(nBu)(OnPr)₂]₂, SiH₂[CH₂—Si(nBu)(OiPr)₂]₂,SiH₂[CH₂—Si(nBu)(OnBu)₂]₂, SiH₂[CH₂—Si(nBu)(OtBu)₂]₂,SiH₂[CH₂—Si(nBu)(OiBu)₂]₂, SiH₂[CH₂—Si(tBu)(OMe)₂]₂,SiH₂[CH₂—Si(tBu)(OEt)₂]₂, SiH₂[CH₂—Si(tBu)(OnPr)₂]₂,SiH₂[CH₂—Si(tBu)(OiPr)₂]₂, SiH₂[CH₂—Si(tBu)(OnBu)₂]₂,SiH₂[CH₂—Si(tBu)(OtBu)₂]₂, SiH₂[CH₂—Si(tBu)(OiBu)₂]₂,SiH₂[CH₂—Si(iBu)(OMe)₂]₂, SiH₂[CH₂—Si(iBu)(OEt)₂]₂,SiH₂[CH₂—Si(iBu)(OnPr)₂]₂, SiH₂[CH₂—Si(iBu)(OiPr)₂]₂,SiH₂[CH₂—Si(iBu)(OnBu)₂]₂, SiH₂[CH₂—Si(iBu)(OtBu)₂]₂,SiH₂[CH₂—Si(iBu)(OiBu)₂]₂, SiH₂[CH₂—Si(SiMe₃)(OMe)₂]₂,SiH₂[CH₂—Si(SiMe₃)(OEt)₂]₂, SiH₂[CH₂—Si(SiMe₃)(OnPr)₂]₂,SiH₂[CH₂—Si(SiMe₃)(OiPr)₂]₂, SiH₂[CH₂—Si(SiMe₃)(OnBu)₂]₂,SiH₂[CH₂—Si(SiMe₃)(OtBu)₂]₂, and SiH₂[CH₂—Si(SiMe₃)(OiBu)₂]₂.

The disclosed compounds are synthesized by reacting a Grignard reagenthaving the formula Si(OR′)_(x)H_(y)R_(z)(CH₂MgX) with a quenching agenthaving the formula SiCl_(a)(OR)_(b)(H)_(c), wherein a=1 to 3; b=0 to 3;c=0 to 2; a+b+c=4; x=0 to 3; y=0 to 1; z=0 to 3; x+y+z=3; X═Cl, Br, or I(“halide” atoms); each R is independently a C1 to C5 linear or branchedalkyl group or a trimethylsilyl group; and each R′ is independently a C1to C5 linear or branched alkyl group.

The Grignard reagent and the quenching agent are reacted in a polarsolvent, such as tetrahydrofuran, diethyl ether, or dimethoxyethane. Themolar ratio of Grignard reagent to quenching agent is betweenapproximately 0.8 to approximately 4.5. The number of halide atoms inthe quenching agent further determines the molar ratio of Grignardreagent to quenching agent. For example, if the quenching agent containsone halide atom, the molar ratio of Grignard reagent to quenching agentshould range from 0.8 to 1.5. If the quenching agent contains two halideatoms, the molar ratio of Grignard reagent to quenching agent shouldrange from 1.6 to 3. If the quenching agent contains three halide atoms,the molar ratio of Grignard reagent to quenching agent should range from2.4 to 4.5.

The quenching agent “deactivates” the Grignard reagent by reacting withthe Grignard reagent to produce the disclosed compound and a Mg saltcompound. This quenching action prevents the Grignard reagent fromreacting with itself and producing undesired products, such astrisilacyclohexane compounds. The number of halide molecules in thequenching agent further determines the number of silicon molecules inthe disclosed compound (not including the Si atom in any pendanttrimethylsilyl groups). For example, if the quenching agent contains onehalide atom, the disclosed compound will contain two silicon atoms. Ifthe quenching agent contains two halide atoms, the disclosed compoundwill contain three silicon atoms. If the quenching agent contains threehalide atoms, the disclosed compound will contain four silicon atoms.

In situ quenching occurs when the Grignard reagent, as it forms,immediately reacts with the quenching agent. As will be described inmore detail infra, the quenching agent and theSi(OR′)_(x)H_(y)R_(z)(CH₂X) reactant used to form the Grignard reagentmay be mixed prior to reaction with magnesium, wherein x=0 to 3; y=0 to1; z=0 to 3; x+y+z=3; each R is independently a C1 to C5 linear orbranched alkyl group or a trimethylsilyl group; and each R′ isindependently a C1 to C5 linear or branched alkyl group.

Preferably, the Grignard reagent and quenching agent are mixed in ananhydrous polar solvent, resulting in improved yield. One of ordinaryskill in the art will recognize how to produce the anhydrous polarsolvent. For example, the polar solvent, benzophenone, and sodium may bemixed and refluxed, followed by distillation (referred to as Natreated). Alternatively, the polar solvent may be filtered throughactivated alumina and then degassed by N₂ bubbling.

The Grignard reagent and the quenching agent may be mixed with the polarsolvent at temperatures ranging from approximately 0° C. toapproximately 70° C., preferably from approximately 0° C. toapproximately 50° C. One of ordinary skill in the art will recognizethat the reaction is exothermic and therefore that the temperature ofthe reaction may increase as the reaction progresses. The mixing mayoccur for a duration of approximately 1 hour to approximately 48 hours,preferably for approximately 8 hours. One of ordinary skill in the artwill recognize that the duration of the reaction will depend upon thetemperature and the number of chlorine atoms in the quenching agent,with more chlorine atoms requiring a longer reaction time. One ofordinary skill in the art will further recognize that these reactionsmust be performed in an inert, anhydrous atmosphere, preferably under anitrogen atmosphere.

After mixing, the polar solvent may be removed by distillation. Theremaining material is mixed with a nonpolar solvent, such as pentane,hexane, or heptane, and subsequently filtered to produce the desiredcompound.

Applicants believe that the alkoxy group of the quenching agents causesthe Grignard reagents to preferentially react with the at least oneSi—Cl bond of the quenching agents. In other words, the alkoxy groupacts as a protecting group to the Si atom during the reaction of theGrignard reagent with the quenching agent. Similarly, Applicants havesurprisingly discovered that the hydride ligand of the quenching agentsremains inert during the reaction of Grignard reagent and the quenchingagent, once again causing the Grignard reagent to preferentially reactwith the at least one Si—Cl bond of the quenching agent. The use of thehydrogen or alkoxy group provides the ability of the disclosed synthesismethods to selectively generate the target compound in high yield. Incontrast, as illustrated in the following comparative example, use ofSiCl₄ as the quenching agent yields the undesirable mixture ofSiCl_(4-x)(CH₂—Si(OEt)₃)_(x) (x=1, 2, 3).

In some embodiments, a=2, b=2, and c=0 to produce quenching agentshaving the formula SiCl₂(OR)₂, wherein each R is independently a C1 toC5 linear or branched alkyl group or a trimethylsilyl group. Exemplaryquenching agents include SiCl₂(OMe)₂, SiCl₂(OEt)₂, SiCl₂(OiPr)₂,SiCl₂(OnPr)₂, SiCl₂(OnBu)₂, SiCl₂(OtBu)₂, SiCl₂(OsBu)₂,SiCl₂(OPentane)₂, or SiCl₂(OSiMe₃)₂. These quenching agents are notcommercially available, but may be synthesized by methods known in theart.

In some embodiments, b=0 to produce quenching agents having the formulaSiCl_(a)(H)_(4-z), wherein a=1 to 1 Exemplary quenching agents includeSiClH₃, SiH₂Cl₂, or SiHCl₃. These quenching agents are commerciallyavailable.

In some embodiments, c=2 to produce quenching agents having the formulaSiCl_(a)(OR)_(2-a)H₂, wherein a=1-2 and each R is independently a C1 toC5 linear or branched alkyl group or a trimethylsilyl group. Exemplaryquenching agents include SiH₂Cl₂, SiH₂Cl(OMe), SiH₂Cl(OEt),SiH₂Cl(OiPr), SiH₂Cl(OnPr), SiH₂Cl(OnBu), SiH₂Cl(OtBu), SiH₂Cl(OsBu),SiH₂Cl(O-Pentane), or SiH₂Cl(OSiMe₃). These quenching agents arecommercially available.

In some embodiments, b=0 and c=2 to produce the quenching agent SiCl₂H₂.This quenching agent is commercially available.

In some embodiments, x=3, y=0, z=0, and R′=Me or Et to produce Grignardreagents having the formula Si(OMe)₃(CH₂MgX) or Si(OEt)₃(CH₂MgX),wherein X═Cl, Br, or I. Exemplary reagents include Si(OMe)₃(CH₂MgCl),Si(OEt)₃(CH₂MgCl), Si(OMe)₃(CH₂MgBr), Si(OEt)₃(CH₂MgBr),Si(OMe)₃(CH₂MgI), and Si(OEt)₃(CH₂MgI).

In some embodiments, y=1 to produce Grignard reagents having the formulaSiH(OR′)_(x)(R)_(2-x)(CH₂MgX), wherein x=0 to 2; X═Cl, Br, or I; each Ris independently a C1 to C5 linear or branched alkyl group or atrimethylsilyl group; and each R′ is independently a C1 to C5 linear orbranched alkyl group. Exemplary reagents include SiH(OMe)₂(CH₂MgCl),SiH(OMe)₂(CH₂MgBr), SiH(OMe)₂(CH₂MgI), SiH(OEt)₂(CH₂MgCl),SiH(OEt)₂(CH₂MgBr), SiH(OEt)₂(CH₂MgI), SiH(OiPr)₂(CH₂MgCl),SiH(OiPr)₂(CH₂MgBr), SiH(OiPr)₂(CH₂MgI), SiH(OnPr)₂(CH₂MgCl),SiH(OnPr)₂(CH₂MgBr), SiH(OnPr)₂(CH₂MgI), SiH(OnBu)₂(CH₂MgCl),SiH(OnBu)₂(CH₂MgBr), SiH(OnBu)₂(CH₂MgI), SiH(OtBu)₂(CH₂MgCl),SiH(OtBu)₂(CH₂MgBr), SiH(OtBu)₂(CH₂MgI), SiH(OMe)(Me)(CH₂MgCl),SiH(OMe)(Me)(CH₂MgBr), SiH(OMe)(Me)(CH₂MgI), SiH(OEt)(Et)(CH₂MgCl),SiH(OEt)(Et)(CH₂MgBr), SiH(OEt)(Et)(CH₂MgI), SiH(OiPr)(iPr)(CH₂MgCl),SiH(OiPr)(iPr)(CH₂MgBr), SiH(OiPr)(iPr)(CH₂MgI),SiH(OnPr)(nPr)(CH₂MgCl), SiH(OnPr)(nPr)(CH₂MgBr),SiH(OnPr)(nPr)(CH₂MgI), SiH(OnBu)(nBu)(CH₂MgCl),SiH(OnBu)(nBu)(CH₂MgBr), SiH(OnBu)(nBu)(CH₂MgI),SiH(OtBu)(tBu)(CH₂MgCl), SiH(OtBu)(tBu)(CH₂MgBr),SiH(OtBu)(tBu)(CH₂MgI), SiH(OMe)(SiMe₃)(CH₂MgCl),SiH(OMe)(SiMe₃)(CH₂MgBr), SiH(OMe)(SiMe₃)(CH₂MgI), SiHMe₂(CH₂MgCl),SiHMe₂(CH₂MgBr), SiHMe₂(CH₂MgI), SiHEt₂(CH₂MgCl), SiHEt₂(CH₂MgBr),SiHEt₂(CH₂MgI), SiH(iPr)₂(CH₂MgCl), SiH(iPr)₂(CH₂MgBr),SiH(iPr)₂(CH₂MgI), SiH(nPr)₂(CH₂MgCl), SiH(nPr)₂(CH₂MgBr),SiH(nPr)₂(CH₂MgI), SiH(nBu)₂(CH₂MgCl), SiH(nBu)₂(CH₂MgBr),SiH(nBu)₂(CH₂MgI), SiH(tBu)₂(CH₂MgCl), SiH(tBu)₂(CH₂MgBr),SiH(tBu)₂(CH₂MgI), SiH(SiMe₃)₂(CH₂MgCl), SiH(SiMe₃)₂(CH₂MgBr), orSiH(SiMe₃)₂(CH₂MgI).

In some embodiments, z=0 to produce Grignard reagents having the formulaSi(OR′)_(x)H_(y)(CH₂MgX), wherein x=0 to 3; y=0 to 1; x+y=3; X═Cl, Br,or I; and each R′ is independently a C1 to C5 linear or branched alkylgroup. Exemplary reagents include Si(OMe)₃(CH₂MgCl), Si(OEt)₃(CH₂MgCl),Si(OMe)₃(CH₂MgBr), Si(OEt)₃(CH₂MgBr), Si(OMe)₃(CH₂MgI),Si(OEt)₃(CH₂MgI), Si(OiPr)₃(CH₂MgCl), Si(OiPr)₃(CH₂MgBr),Si(OiPr)₃(CH₂MgI), Si(OnPr)₃(CH₂MgCl), Si(OnPr)₃(CH₂MgBr),Si(OnPr)₃(CH₂MgI), SiH(OMe)₂(CH₂MgCl), SiH(OMe)₂(CH₂MgBr),SiH(OMe)₂(CH₂MgI), SiH(OEt)₂(CH₂MgCl), SiH(OEt)₂(CH₂MgBr),SiH(OEt)₂(CH₂MgI), SiH(OiPr)₂(CH₂MgCl), SiH(OiPr)₂(CH₂MgBr),SiH(OiPr)₂(CH₂MgI), SiH(OnPr)₂(CH₂MgCl), SiH(OnPr)₂(CH₂MgBr),SiH(OnPr)₂(CH₂MgI), SiH(OnBu)₂(CH₂MgCl), SiH(OnBu)₂(CH₂MgBr),SiH(OnBu)₂(CH₂MgI), SiH(OtBu)₂(CH₂MgCl), SiH(OtBu)₂(CH₂MgBr), orSiH(OtBu)₂(CH₂MgI).

The Grignard reagents may be synthesized by reactingSi(OR′)_(x)H_(y)R_(z)(CH₂X) over magnesium, wherein x=0 to 3; y=0 to 1;z=0 to 3; x+y+z=3; each R is independently a C1 to C5 linear or branchedalkyl group or a trimethylsilyl group; and each R′ is independently a C1to C5 linear or branched alkyl group. The Si(OR′)_(x)H_(y)R_(z)(CH₂X)reactants are commercially available.

The synthesis of the Grignard reagent may occur in the same vessel asthat in which the Grignard reagent and the quenching agent are reacted.The Si(OR′)_(x)H_(y)R_(z)(CH₂X) reactant and quenching agent may bemixed together before reaction with magnesium. Alternatively, theSi(OR′)_(x)H_(y)R_(z)(CH₂X) reactant may be added to the Grignardreagent, followed by addition of the quenching agent. One of ordinaryskill in the art will recognize that addition of an activator, such as1,2-dibromoethane (BrCH₂CH₂Br), iodide (I₂), or pure HCl, may be neededto activate the Mg surface. The activator may be added to the Grignardreagent before addition of the Si(OR′)_(x)H_(y)R_(z)(CH₂X) reactantand/or quenching agent.

The OR′ alkoxy group of the Si(OR′)_(x)H_(y)R_(z)(CH₂X) reactant is morereactive than the R alkyl group. As a result, upon exposure to Mg, theSi(OR′)_(x)H_(y)R_(z)(CH₂X) reactant may react upon itself to form thecyclic molecule (—CH₂—Si(OR′)_(x)H_(y)R_(z)—)₃. Therefore, when thereactant contains at least one alkoxy group, the synthesis of theGrignard reagent preferably occurs in the same vessel as that in whichthe reaction between the Grignard reagent and the quenching agentoccurs. In this embodiment, the Si(OR′)_(x)H_(y)R_(z)(CH₂X) reactant,Mg, and the quenching agent are added to a flask containing the polarsolvent and mixed (i.e., in situ quenching). The Mg may be activated byan activator prior to adding the Si(OR′)_(x)H_(y)R_(z)(CH₂X) reactantand the quenching agent. The quenching agent prevents the Grignardreagent formed by the reaction of the Si(OR′)_(x)H_(y)R_(z)(CH₂X)reactant and the Mg from reacting with itself and producing undesiredproducts, such as trisilacyclohexane compounds. The quenching agent“deactivates” the Grignard reagent by reacting with the Grignard reagentto produce the disclosed compound and a Mg salt compound. The mixing mayoccur at temperatures ranging from approximately 0° C. to approximately70° C., preferably from approximately 0° C. to approximately 50° C. Oneof ordinary skill in the art will recognize that the reaction isexothermic and therefore that the temperature of the reaction mayincrease as the reaction progresses. The mixing is completed when no Mgremains.

After mixing, the polar solvent may be removed by distillation. Theremaining material is mixed with a nonpolar solvent, such as pentane,butane, or hexane, and subsequently filtered to produce the desiredcompound.

The synthesized compounds may be reduced to form a compound having theformula SiH_(b+c)[CH₂—SiH_(x+y)R_(z)]_(4−b−c), wherein b=0 to 3; c=0 to2; b+c=1 to 3; x=0 to 3; y=0 to 1; z=0 to 3; x+y+z=3; and each R isindependently a C1 to C5 linear or branched alkyl group or atrimethylsilyl group. AlLiH₄ in ether may be used as the reducing agent.The molar ratio of AlLiH₄ toSi(OR)_(b)(H)_(c)[CH₂—Si(OR′)_(x)H_(y)R_(z)], is between approximately(b+ax)/4 and approximately (b+ax)/2, wherein b=0 to 3, a=1 to 3, and x=0to 3. Preferably, the molar ratio of AlLiH4 toSi(OR)_(b)(H)_(c)[CH₂—Si(OR′)_(x)H_(y)R_(z)]_(a) is approximately1.2[(b+ax)/4] to approximately 1.5[(b+ax)/4]. NaBH₄ in ether mayalternately be used as the reducing agent. The molar ratio of NaBH₄ toSi(OR)_(b)(H)_(c)[CH₂—Si(OR)_(x)H_(y)R]_(a) is between (b+ax)/4 andapproximately (b+ax)/2, wherein b=0 to 3, a=1 to 3, and x=0 to 3.Preferably, the molar ratio of AlLiH4 toSi(OR)_(b)(H)_(c)[CH₂—Si(OR′)_(x)H_(y)R_(z)]_(a) is approximately1.2[(b+ax)/4] to approximately 1.5[(b+ax)/4]. During reduction, the atleast one alkoxy group of the quenching agent that had formerly acted asa protecting group is reactive to the reducing agent and easily reducedto H.

In one preferred embodiment, Si(OEt)₂[CH₂—Si(OEt)₃]₂ is synthesized byreacting a Grignard reagent having the formula Si(OEt)₃(CH₂MgCl) with acompound having the formula Si(OEt)₂Cl₂. The Si(OEt)₃(CH₂MgCl) Grignardreagent is formed in situ by reacting Si(OEt)₃(CH₂Cl) over magnesium.Addition of an activator may be necessary to activate the Mg surface.The Si(OEt)₃(CH₂MgCl) Grignard reagent may be formed in the same vesselas that in which the Grignard reagent and the quenching agent arereacted. Preferably, the Si(OEt)₃(CH₂MgCl) Grignard reagent is formed inthe same vessel as that in which the Grignard reagent and the quenchingagent are reacted.

Si(OEt)₂[CH₂—Si(OEt)₃]₂ may be reduced to form a compound having theformula SiH₂[CH₂—SiH₃]₂. AlLiH₄ in ether may be used as the reducingagent. The molar ratio of AlLiH₄ to Si(OEt)₂[CH₂—Si(OEt)₃]₂ isapproximately 2. Alternatively, NaBH₄ in ether may be the reducingagent. The molar ratio of NaBH₄ to Si(OEt)₂[CH₂—Si(OEt)₃]₂ isapproximately 2.

EXAMPLES

The following examples illustrate experiments performed in conjunctionwith the disclosure herein. The examples are not intended to be allinclusive and are not intended to limit the scope of disclosuredescribed herein.

Comparative Example

2 molar equivalents ClCH₂Si(OEt)₃, 2 molar equivalents of Mg (sandedribbon) and 1 molar equivalent of SiCl₄ were mixed with tetrahydrofuran(THF) (Na treated) in flask. The mixture was stirred until Mgdisappeared and THF was removed by distillation. Pentane was added toextract a mixture including the (EtO)₃SiCH₂Si(Cl)₂CH₂Si(OEt)₃ product.After removal of pentane, 71% crude yield was obtained, includingimpurities formed by the reaction of 3 ClMgCH₂—Si(OEt)₃ molecules withSiCl₄, yielding SiCl(CH₂—Si(OEt)₃)₃.

Upon reduction by AlLiH₄ in ether, the obtained reduced mixture (all Clor OEt being substituted by H to form the target compoundH₃SiCH₂SiH₂CH₂SiH₃) is analyzed by gas chromatography shown in FIG. 1,showing a large concentration of branched carbosilane SiH(CH₂—SiH₃)₃ andpartially reacted product (CH₂(SiH₃)₂).

Example 1

2 molar equivalents of ClCH₂Si(OEt)₃, 2 molar equivalents of Mg (sandedribbon), and molar 1 equivalent of SiCl₂(OEt)₂ were added in flask withTHF (Na treated) under N₂. The mixture was stirred at room temperatureuntil Mg disappeared. THF was removed by distillation. Pentane was addedto extract the intermediate and then filtered to separate solid. Afterdistillation of pentane, >90% yield crude(EtO)₃Si—CH₂—Si(OEt)₂-CH₂—Si(OEt)₃ was obtained.(EtO)₃Si—CH₂—Si(OEt)₂-CH₂—Si(OEt)₃ was directly reduced without furtherpurification by 3 molar equivalents (based on the amount of(EtO)₃Si—CH₂—Si(OEt)₂-CH₂—Si(OEt)₃) of LiAlH₄ in ether in ice bath underN₂. The mixture was stirred for ˜6 hours at room temperature. Thevolatiles were separated from solid by-products and LiAlH₄ by vacuumtransfer, and ether was removed from the collected volatives bydistillation using a 55° C. bath. The final distillation give puretrisilapentane (TSP) as 70% overall yield. The pure TSP was analysed byGC as shown in FIG. 2, which indicates no undesired by-products remain.TSP: 1H NMR (C6D6): δ 3.95 (p, 2H, SiH2), 3.67 (t, 6H, SiH3), −0.40 (m,4H, CH2). MS, m/z: 120 [M+].

Example 2

A 3-neck 100 mL flask equipped with a dry ice condenser, gas inlettubing adapter, and a gas inlet adapter was charged with 50 mL of THF.The flask was cooled by dry ice to −40° C., the dry ice condenser wasalso filled with dry ice. 4.6 g (0.045 mol) of DCS (SiH₂Cl₂) wascondensed into the flask using mass flow controller with a flow rate of180-190 mL/min. 19.4 g (0.091 mol) of (OEt)₃SiCH₂Cl was added to the DCSsolution by syringe. A 250 mL 3-neck flask equipped with a dry icecondenser, thermometer, and torion 14 adapter was charged with Mgturnings (2.21 g, 0.091 mol) and 50 mL of THF. The mixture was cooled byice bath to 5° C., and the condenser was filled with dry ice. Thesolution of DCS and (OEt)₃SiCH₂Cl was slowly added to Mg suspension via22 gauge canula. After ˜10 mL of the solution was added, 0.1 mL ofBrCH₂CH₂Br was added to the reaction mixture to initiate the reaction.The rest of DCS solution was added within 30 min. The mixture wasstirred at 5° C. for ˜2 h. The ice bath was removed and the mixture waswarmed up to room temperature while maintaining the dry ice condenserfilled with dry ice. The mixture was stirred for 3 days at roomtemperature before all Mg disappeared. The mixture was filtered throughCelite brand diatomaceous earth. The solids were washed with 2×20 mL ofpentane. The solvents were removed from the filtrate under vacuum. Theresidue was mixed with 50 mL of pentane, and the mixture was filteredthrough Celite brand diatomaceous earth to remove the rest of thesolids. Pentane was removed from the clear yellowish filtrate undervacuum leaving 10.4 g of (EtO)₃Si—CH₂—SiH₂—CH₂—Si(OEt)₃ (the targetcompound) and un-reacted (OEt)₃SiCH₂Cl (60% yield of the targetcompound).

The target compound was reduced using AlLiH₄ (2.4 equivalents) indiethlylether similarly to the other example, yielding1,3,5-trisilapetane.

While embodiments of this invention have been shown and described,modifications thereof can be made by one skilled in the art withoutdeparting from the spirit or teaching of this invention. The embodimentsdescribed herein are exemplary only and not limiting. Many variationsand modifications of the composition and method are possible and withinthe scope of the invention. Accordingly the scope of protection is notlimited to the embodiments described herein, but is only limited by theclaims which follow, the scope of which shall include all equivalents ofthe subject matter of the claims.

We claim:
 1. A method of synthesizing a carbosilane compound comprisingreacting a Grignard reagent having the formula Si(OEt)₃(CH₂MgCl) with aquenching agent having the formula Si(OEt)₂Cl₂ to produceSi(OEt)₂[CH₂—Si(OEt)₃]₂.
 2. The method of claim 1, further comprisingforming the Grignard reagent Si(OEt)₃(CH₂MgCl) by reactingSi(OEt)₃(CH₂X) over magnesium.
 3. The method of claim 2, wherein thestep of forming the Grignard reagent Si(OEt)₃(CH₂MgCl) occurs in a samevessel as the step of reacting the Grignard reagent and the quenchingagent.
 4. The method of claim 1, further comprising reducingSi(OEt)₂[CH₂—Si(OEt)₃]₂ to form a compound having a formulaSiH₂[CH₂—SiH₃]₂.